Pest control formulations and methods of making and using same

ABSTRACT

Compositions useful for controlling pests are disclosed. In some embodiments, the composition includes a pesticidal natural oil and a polar aromatic solvent or an alkyl alcohol solvent. Methods of making and using the compositions are disclosed.

REFERENCE TO RELATED APPLICATIONS

This application is a divisional of U.S. patent application Ser. No.14/248,189 filed 8 Apr. 2014, which is a continuation-in-part of U.S.patent application Ser. No. 14/347,219 filed 4 Oct. 2012, which is a 371of Patent Cooperation Treaty patent application No. PCT/IB2012/055348filed 4 Oct. 2012, which claims the benefit of each of U.S. provisionalpatent application No. 61/542,993 filed 4 Oct. 2011, US provisionalpatent application No. 61/622,893 filed 11 Apr. 2012, and US provisionalpatent application No. 61/652,110 filed 25 May 2012. Each of theforegoing applications is hereby incorporated by reference herein in itsentirety.

TECHNICAL FIELD

Some embodiments of the present invention pertain to compositions thatcan be used to control a variety of pests. Some embodiments of thepresent invention can be used to control arthropods, including insectsand arachnids, and/or other pests. Some embodiments of the presentinvention can be used to control sucking and biting pests, includinge.g. bed bugs, mosquitoes, ticks, lice, stink bugs, flies, cockroachesand moths. Some embodiments of the invention pertain to methods of usingcompositions to control pests. Other embodiments of the inventionpertain to methods of making compositions to control pests.

BACKGROUND

Pest control is an ongoing, worldwide problem. In addition to physicalmeans of control that have been practiced for centuries, recent decadeshave witnessed the emergence and widespread use of hundreds ofchemically developed pest repellents, growth regulators, andinsecticides. These products are frequently synthetic varieties that areheavily refined prior to commercialization—the list includes thepyrethroids (including deltamethrins, cyfluthryns, etc), DEET and otheraromatic amides, organophosphates, and carbamates. The usefulness ofthese products is often limited by factors including human orenvironmental toxicity, insect resistance (particularly to pyrethroids;see e.g. Romero, et al.), limited dry residue activity, repellancy andphysical factors that make them inappropriate for indoor use (odor,staining). For these reasons and due to shifting consumer preferenceparadigms, there is consistently increasing demand fornaturally-derived, effective pest control products that overcome theselimitations.

Some pesticide products are derived from botanical and other naturalsources; for example the pyrethrin classes of pesticides are derivedfrom the pyrethrum daisy, Chrysanthemum cinerariaefolium. Other examplesinclude: rotenone, from the roots of Derris Lonchocarpus; ryania, fromthe stems of Ryania speciosa; and neem, derived from the leaves, bark,and seeds of Azadirachta indica.

The tree Azadirachta indica—in some cases referred to as the “SacredTree” or “Nature's Pharmacy”—has long been recognized as a source of awide variety of useful bioactive compounds. Neem derivatives havedemonstrated effectiveness as moisturizing agents, and neem oil itselfhas been used as a treatment for various skin conditions including acne,psoriasis, and chicken pox. It is also used in toothpastes, as a cookingingredient, and in pharmaceuticals for treating a range of symptomsincluding fever, earache, headache, and serious disorders includingdiabetes (see e.g. Brachmachari). In the agricultural sector, neem oilis considered an effective measure for the prevention of mildew,anthracnose, rust, leaf spot, botrytis, scab and alternaria. Itsderivatives have furthermore been described variously as antiviral,antimicrobial, antifungal, and antiseptic. Neem oil and many of itsderivatives have also been recognized and used as insect control agentsand pesticides.

Neem oil contains dozens of active compounds that kill or repel insects,with demonstrated efficacy against more than 375 insect species. It hasbeen recognized as a repellent of many pests, particularly insects (seee.g. Mishra, et al). At higher concentrations it has been reported todemonstrate repellency activity against some insects for up to sixmonths after application (see Daniel & Smith). These repellencycharacteristics limit neem oil's insecticidal activity significantly,since insects are repelled from exposure to the very product that isintended to be insecticidal. Neem oil has been shown to prevent eggemergence of some insects when eggs are treated directly with the oil:See Rahman & Talukder; Ahmed, et al. Neem oil also demonstrates someprevention of oviposition—of a limited subset of insects—at higherconcentrations (including the maize weevil; see M K Khattak).

Current hypotheses suggest that neem oil may work as a contact killer,as an antifeedant, as an insect-growth regulator, a sterilizing agent, agut motility inhibitor, and/or as a chitin inhibitor. Azadirachtin—animportant active ingredient in neem oil—has been reported to exhibitantifeedant, repellent, and sterilization activities under certaincircumstances and has been used as a pest control chemical in the past(see U.S. Pat. No. 4,556,562).

Neem oil and azadirachtin are believed to exhibit complex mechanisms ofinsect toxicity, including activity upon insect hormonal systems,antifeedant activity, anti-molting activity, and numerous otheractivities. Neem oil as a pesticide is biodegradable and of lowenvironmental and human toxicity, exempted from the tolerancerequirement by the United States EPA (see United States FederalRegister, Volume 60, Number 239, 1995).

Neem oil has drawbacks as an insecticide. While effective at preventingmolting and exhibiting certain repellency characteristics in someinsects, reports of neem oil's knockdown capability are inconsistent(see e.g. Schumutter), and some studies find it less efficient atkilling adult insects than related pesticides (see Pavela). Neem oil hasbeen reported to have poor dry residue pesticidal activity against mostinsects, and poor dry residual prevention of egg emergence andprevention of oviposition against most species of insects. Neem oil hasan odor that is offensive to some people, and its odor does not rapidlydisperse.

Other natural oils have been reported to exhibit insecticidal or otherpest control activities, as are described further below.

Pests are a considerable annoyance and health risk. For example, inrecent years, there has been a resurgence of bed bug (Cimex lectulariusL.) infestations across North America. Bed bugs cause sleeplessness,anxiety, and discomfort for those affected. Bed bugs are troublesomepests. They live and hide in crevices, seams and other small spaces.They are hard to identify and locate, and can survive dormant for monthsor a year or more without feeding. They spread by clinging to suitcases,furniture and clothing which people bring with them from place to place.Current methods of bed bug control are expensive and have variouslimitations, particularly because products must be applied in sleepingareas where the affected individuals are subject to close and lengthyexposure.

There remains a need for improved pesticides derived from naturalsources, pesticides that can prevent egg eclosion, and pesticides havingimproved dry residue and prolonged residual activity.

SUMMARY

Some embodiments of the present invention provide pesticidalcompositions containing a pesticidal natural oil and/or a componentthereof and/or a derivative thereof and a polar aromatic solvent. Someembodiments can be used to control pests by killing the pests,preventing or reducing feeding, preventing or reducing oviposition,preventing or reducing eclosion of their eggs, or the like. Someembodiments exhibit effective or more rapid knockdown pesticidalactivity, dry residue pesticidal activity and/or prolonged residualpesticidal activity. Some embodiments can be used to control pestsincluding insects and/or arachnids, including arthropods such as bedbugs.

In some embodiments, the pesticidal natural oil is neem oil, clove oil,peppermint oil, mint oil, cinnamon oil, thyme oil, oregano oil, and/orgarlic oil and/or derivatives or extracts thereof. In some embodiments,the polar aromatic solvent is selected from the group consisting of:aryl ketones, aryl alcohols, aryl-alkyl alcohols, aryl aldehydes,aryl-alkyl ketones, aryl-aryl ketones, aryl carboxylic acids, arylesters, aryl-alkyl esters, aryl-aryl esters, aryl-alkyl ethers, andaryl-aryl ethers. In some embodiments, the polar aromatic solvent is anaryl ketone such as acetophenone. In some embodiments, the polararomatic solvent is acetophenone, benzyl alcohol, ethyl benzoate and/orbenzoic acid. In some embodiments, the pesticidal natural oil is neemoil and the polar aromatic solvent is acetophenone.

In some embodiments, the combination of the natural pesticidal oil andthe polar aromatic solvent exhibits a synergistic level of pesticidalactivity. In some embodiments, the combination of the pesticidal naturaloil and the polar aromatic solvent is effective as a pesticide whereineach of the pesticidal natural oil and the polar aromatic solvent arepresent at a concentration below the concentration at which thepesticidal natural oil or the polar aromatic solvent would exhibitsimilar pesticidal activity if used alone. In some such embodiments, thepolar aromatic solvent is acetophenone and the pesticidal natural oil isneem oil, clove oil, cinnamon oil, thyme oil, oregano oil and/or garlicoil.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows the results of an example testing the prevention of eggemergence by a composition in accordance with one embodiment of theinvention.

FIG. 2 shows the results of an example testing the prevention ofcockroach egg emergence by a composition according to one exampleembodiment.

FIG. 3 shows the results of an example testing the ability of acomposition in accordance with one embodiment of the invention to killpyrethroid-resistant bed bugs.

DETAILED DESCRIPTION

Throughout the following description specific details are set forth inorder to provide a more thorough understanding to persons skilled in theart. However, well known elements may not have been shown or describedin detail to avoid unnecessarily obscuring the disclosure. Accordingly,the description and drawings are to be regarded in an illustrative,rather than a restrictive, sense.

Where a range of values is provided, it is understood that eachintervening value, to the tenth of the unit of the lower limit unlessthe context clearly dictates otherwise, between the upper and lowerlimit of that range and any other stated or intervening value withinthat stated range is encompassed within embodiments of the invention.The upper and lower limits of these smaller ranges may independentlydefine a smaller range of values, and it is to be understood that thesesmaller ranges are intended to be encompassed within embodiments of theinvention, subject to any specifically excluded limit in the statedrange.

Unless defined otherwise, all technical and scientific terms used hereinhave the same meaning as commonly understood by one of ordinary skill inthe art to which this invention belongs. Although any methods andmaterials similar or equivalent to those described herein can also beused in the practice or testing of embodiments of the present invention,preferred methods and materials are described to avoid unnecessarilyobscuring the disclosure.

As used herein, “comprises” or “comprising” are to be interpreted intheir open-ended sense, i.e. as specifying that the stated features,elements, steps or components referred to are present, but not excludingthe presence or addition of further features, elements, steps orcomponents.

As used herein, singular forms include plural references unless thecontext clearly dictates otherwise. For example, “a fungus” alsoencompasses “fungi”.

As used herein, the term “pest” refers to organisms that negativelyaffect a host-such as a plant or an animal such as a mammal—bycolonizing, damaging, attacking, competing with them for nutrients, orinfecting them. This includes arthropods including insects andarachnids, and includes sucking and biting pests such as bed bugs,mites, ticks, ants, lice, and cockroaches.

As used herein, the term “pesticide” refers to an agent that can be usedto control and/or kill a pest. The term is understood to encompass, butis not limited to, naturally occurring or synthetic chemicalinsecticides (larvicides, adulticides, ovicides), acaricides(miticides), fungicides, nematicides, parasiticides, or other controlagents. “Pesticidal activity” refers to an agent that is active as apesticide.

As used herein, the term “egg emergence” means eclosion; that is, theemergence of an adult insect from its pupal case or the hatching of aninsect larva/nymph from an egg. “Preventing eclosion” or “preventing eggemergence” means preventing or delaying the emergence of an adult insectfrom its pupal case or the hatching of an insect larva from an egg.

As used herein, the terms “control” or “controlling” are meant toinclude, but are not limited to, any killing, growth regulating, orpestistatic (inhibiting or otherwise interfering with the normal lifecycle of the pest) activities of a composition against a given pest.These terms include for example sterilizing activities which prevent theproduction of ova or sperm, including preventing vitellogenesis, causedeath of sperm or ova, or otherwise cause severe injury to the geneticmaterial. Further activities intended to be encompassed within the scopeof the terms “control” or “controlling” include preventing larvae fromdeveloping into mature progeny, modulating the emergence of pests fromeggs including deterring oviposition, preventing eclosion, degrading theegg material, suffocation, reducing gut motility, inhibiting theformation of chitin, disrupting mating or sexual communication, andpreventing feeding (antifeedant) activity.

As used herein, the terms “repellent” or “repelling” mean that acomposition discourages pests from landing or climbing on a surface towhich the composition has been applied or incorporated, and/or that thecomposition encourages pests to move away from a surface to which thecomposition has been applied or incorporated.

As used herein, a “pesticidal natural oil” is a natural oil or oils, forexample derived from plant material, that exhibits pesticidal activityeither on its own or in combination with a solvent. As used herein,“pesticidal natural oil” includes other materials derived, extracted orotherwise obtained from natural sources, for example, powdered extractsand the like. A “derivative” is a compound or composition that can beobtained from a natural oil. A “constituent” or “component” is acompound or composition found in a natural oil.

As used herein, “neem oil” refers to oil derived from the seeds, leaves,and bark of Azadirachta indica. Methods for obtaining neem oil,azadirachtin extract or other derivatives purified from neem oil areknown in the art. One exemplary method for obtaining neem oil is coldpressing.

As used herein, “dry residue activity” refers to compositions thatexhibit pesticidal activity and/or prevention of egg emergence after thecomposition has dried for at least two hours from application beforepests are exposed to the dry reside.

As used herein, “prolonged residual activity” refers to compositionsthat exhibit pesticidal activity and/or prevention of egg emergence upto several days after the composition has been applied to a targetsurface. In some embodiments, “prolonged residual activity” refers tocompositions that exhibit pesticidal activity and/or prevention of eggemergence up to one week, two weeks, three weeks, or more after thecomposition has dried after being applied to a target surface. Higherprolonged residual pesticidal activity can extend the interval betweenre-treatments of a target surface necessary to achieve an acceptablelevel of pest control. In some embodiments, prolonged residual activityrefers to compositions that exhibit pesticidal activity and/orprevention of egg emergence up to at least 7 days, 8 days, 9 days, 10days, 11 days, 12 days, 13 days, 14 days, 15 days, 16 days, 17 days, 18days, 19 days, 20 days, or 21 days after treatment, meaning that acomposition does not need to be re-applied to pests or to surfaces wherethe pests or their eggs may contact or otherwise be exposed to thecomposition for at least such period of time.

As used herein, “knockdown” activity refers to the pesticidal activityof a composition as applied directly to a pest.

As used herein, “surface” or “target surface” includes a surface towhich a pesticide is applied or is to be applied. Such surfaces mayinclude, for example, a surface where pests are likely to contact orotherwise be exposed to the applied pesticide, to lay their eggs, and/ora surface that has been or is suspected to be infested by pests.

As used herein, “preventing oviposition” means that a compositionprevents a pest from laying eggs, and/or decreases the number of eggstypically laid by a pest.

As used herein, the term “stability” means the ability of a compositionto retain its pesticidal activity after application to a surface to betreated with insecticide.

The term “carrier” as used herein refers to an inert material, organicor inorganic, with which an active ingredient can be mixed or formulatedto facilitate its application, storage, transport, and/or handling, orimprove various product characteristics such as its odor. Commonly usedcarriers include, but are not limited to, ethanol, isopropanol, otheralcohols, and water. Exemplary carriers that can be used in someembodiments of the invention include inert carriers listed by the U.S.EPA as a Minimal Risk Inert Pesticide Ingredients (4A), Inert PesticideIngredients (4B) or under EPA regulation 40 CFR 180.950, each of whichis hereby incorporated herein by reference in its entirety for allpurposes, including for example, citric acid, lactic acid, glycerol,castor oil, benzoic acid, carbonic acid, ethoxylated alcohols,ethoxylated amides, glycerides, benzene, butanol, 1-propanol, hexanol,other alcohols, dimethyl ether, and polyethylene glycol.

Some embodiments of the present invention provide compositions andmethods useful in the control of a variety of pests. Some embodiments ofthe present invention can be used to control insects, arachnids,centipedes, millipedes and/or other pests. Some embodiments of thepresent invention can be used to control sucking and biting pests,including e.g. bed bugs, mosquitoes, ticks, lice, fleas, stink bugs,flies, cockroaches, spiders and/or moths.

In some embodiments, the composition includes a combination of apesticidal natural oil and a polar aromatic solvent. In someembodiments, the combination of the pesticidal natural oil and the polararomatic solvent is effective to control pests. In some embodiments, thecombination of the pesticidal natural oil and the polar aromatic solventis effective to prevent eclosion. In some embodiments, the combinationof the pesticidal natural oil and the polar aromatic solvent iseffective to prevent oviposition. In some embodiments, the combinationof the pesticidal natural oil and the polar aromatic solvent exhibitseffective knockdown pesticidal activity. In some embodiments, thecombination of the pesticidal natural oil and the polar aromatic solventexhibits prolonged residual pesticidal activity.

In some embodiments, the combination of the pesticidal natural oil andthe polar aromatic solvent exhibits markedly improved ability to controlpests and/or an expanded range of pesticidal activity as compared witheither the pesticidal natural oil or the polar aromatic solvent alone.In some embodiments, a composition including a combination of apesticidal natural oil and a polar aromatic solvent exhibits improveddry residue pesticidal activity as compared with either the pesticidalnatural oil or the polar aromatic solvent used alone. In someembodiments, a composition including a combination of a pesticidalnatural oil and a polar aromatic solvent acts to prevent eclosion whenused under conditions at which the pesticidal natural oil or the polararomatic solvent used alone would not prevent eclosion to a significantlevel. In some embodiments, a composition including a combination of apesticidal natural oil and a polar aromatic solvent acts to preventoviposition when used under conditions at which the natural oil or thepolar aromatic solvent used alone would not prevent oviposition to asignificant level. In some embodiments, a composition including acombination of a pesticidal natural oil and a polar aromatic solventexhibits improved or more rapid knockdown of a pest as compared witheither the pesticidal natural oil or the polar aromatic solvent usedalone. In some embodiments, a composition including a combination of apesticidal natural oil and a polar aromatic solvent exhibits prolongedresidual pesticidal activity as compared with either the pesticidalnatural oil or the polar aromatic solvent used alone. In someembodiments, a composition including a combination of a pesticidalnatural oil and a polar aromatic solvent exhibits prolonged residual eggeclosion prevention activity, while the pesticidal natural oil or thesolvent used alone do not exhibit such activity.

In some embodiments, a composition including a combination of a polararomatic solvent with a pesticidal natural oil shows a lesser degree ofrepellency than the repellency of the pesticidal natural oil used alone.Under certain experimental conditions described herein, dry residues ofexemplary combinations comprising neem oil in combination with a polararomatic solvent demonstrate significantly less repellency to adult bedbugs than dry residues of neem oil alone, and exhibit comparable levelsof repellency when compared with an untreated control. In someembodiments, the combination of a polar aromatic solvent with apesticidal natural oil appears to mitigate the repellency of the naturaloil (that is, the repellency of a target surface treated with thecombination is the same as the repellency of the untreated targetsurface). In some embodiments, the combination of a polar aromaticsolvent with a pesticidal natural oil appears to mitigate the repellencyand improve the attractancy of the natural oil (that is, a targetsurface treated with the combination is more attractive than theuntreated target surface and/or the treatment flushes pests out ofhiding spots and crevices).

Decreasing the repellency of a pesticidal natural oil (or acting as anattractant) can increase the effectiveness of a composition as apesticide, because pests will remain in an area where the compositionhas been applied (or can be flushed from hiding areas), rather thanmoving to untreated areas due to the repellency of the pesticidalnatural oil, and thereby avoiding or being otherwise unaffected by theproperties of the pesticide. In some cases, applying a product with ahigh degree of repellency can result in the spread of pests, as thepests move away from the location to which the repellent product hasbeen applied. For example, if there is a localized infestation of pestsin a residential dwelling and a repellent product is applied to the areawhere the infestation is localized, the pests may simply move on andinfest other areas of the residential dwelling.

In some embodiments, a pesticidal composition includes two or morenatural oils and a polar aromatic solvent. In some embodiments, at leastone of the natural oils is a pesticidal natural oil, and at least one ofthe natural oils is an oil or fragrance selected to decrease therepellency of the one or more pesticidal natural oils in thecomposition. In some embodiments, the natural oils are selected toprovide a composition that has an odor to humans that is more pleasantthan the odor of the pesticidal natural oil alone, i.e. the natural oilis an additive that masks the odor of the pesticidal natural oil.

In some embodiments, the polar aromatic solvent is a ketone. In someembodiments, the polar aromatic solvent is a simple ketone. In someembodiments, the polar aromatic solvent is acetophenone. In someembodiments, the polar aromatic solvent is an alcohol, an aldehyde, anester, or a carboxylic acid. In some embodiments, the polar aromaticsolvent is an aryl alcohol, an aryl-alkyl alcohol, an aryl aldehyde, anaryl ketone, an aryl-alkyl ketone, an aryl-aryl ketone, an arylcarboxylic acid, an aryl-alkyl ester, an aryl-aryl ester, an aryl-alkylether, an aryl-aryl ether and/or a combination thereof.

In some embodiments, the polar aromatic solvent has the generalstructure

wherein R₁ can be:

and wherein R₂, R₃, R₄, R₅ and R₆ can independently be —H, or an alkylgroup, alkenyl group or alkynyl group, including e.g. a methyl, ethyl,propyl, isopropyl, butyl, or pentyl group or the like, or an —OH groupor a halo functional group, or an alkyl, alkenyl or alkynyl groupincluding an alcohol, halo or other polar functional group; and whereinR₇ and R₈ can independently be —H or an alkyl group, including e.g. amethyl, ethyl, propyl, isopropyl, butyl, or pentyl group or the like, oran aromatic group. In some embodiments, R₇ and/or R₈ can have othersubstituents. In some embodiments R₂, R₃, R₄, R₅ and/or R₆ can haveother substituents. Other polar aromatic compounds could be used in someembodiments.

In some embodiments, the polar aromatic solvent is benzyl alcohol,3,4-dimethylbenzyl alcohol, alpha-4-dimethylbenzyl alcohol,2-phenyl-2-propanol, 1-phenylethanol, benzaldehyde,methylcyclohexylketone, cyclohexanone, p-tolualdehyde,2-hydroxy-5-methyl benzaldehyde, acetophenone, 4′-hydroxyacetophenone,4′-methylacetophenone, 2′-hydroxyacetophenone,2′,4′-dimethylacetophenone, 3′,4′-dimethylacetophenone, propiophenone,4′-methylproppiophenone, butyrophenone, isobutryophenone, valerophenone,4′-hydroxyvalerophenone, cyclohexyl phenyl ketone, hexanophenone,2,2′,4,4′-tetrahydroxybenzophenone, t-tert-butylcyclyhexylacetate,benzoic acid, 4-hydroxy benzoic acid, 4-hydroxy-3-methyl benzoic acid,ethyl benzoate, isobutyl benzoate, benzyl benzoate,propyl-4-hydmxybenzoate, phenol, benzyl methyl ether, butyl phenylether, trans-anethole, dibenzyl ether, diphenyl ether, and/or acombination thereof.

In some embodiments, the polar aromatic solvent is replaced by an alkylalcohol. In some embodiments, the solvent is 2-ethyl-1-hexanol,1-nonanol, 2-butyl-1-octanol, 2-hexyl-1-decanol, 1-dodecanol, 2-octanol,1-decanol, 2-propanol (IPA), cyclohexanol, and/or a combination thereof.

In some embodiments, compositions including a pesticidal natural oil anda polar aromatic solvent exhibit significantly improved stability anddry residue pesticidal activity as compared to the dry residuepesticidal activity of the pesticidal natural oil or the polar aromaticsolvent alone. In one embodiment, the addition of acetophenone or otherpolar aromatic organic solvent to neem oil or a component or derivativeof neem oil provides a composition with significantly improved stabilityand dry residue pesticidal activity as compared with neem oil or itscomponents or derivatives alone, and as compared with the dry residuepesticidal activity of the solvent alone.

In some embodiments, compositions including a pesticidal natural oil anda polar aromatic solvent prevent egg emergence (i.e. prevent eclosion).In some embodiments, compositions including a pesticidal natural oil anda polar aromatic solvent exhibit prolonged egg eclosion preventionactivity.

In some embodiments, a composition including a combination of apesticidal natural oil and a polar aromatic solvent exhibits improvedprevention of oviposition as compared with either the pesticidal naturaloil or polar aromatic solvent alone.

In some embodiments, a composition including a combination of apesticidal natural oil and a polar aromatic solvent exhibits improved ormore rapid knockdown of pests as compared with either the pesticidalnatural oil or polar aromatic solvent alone.

In some embodiments, compositions including a pesticidal natural oil anda polar aromatic solvent exhibit both improved or more rapid knockdownof pests as compared with either the pesticidal natural oil or the polararomatic solvent used alone, and also prolonged dry residual pesticidalactivity.

In some embodiments, the pesticidal natural oil is neem oil or acomponent or derivative thereof. In other embodiments, the pesticidalnatural oil is neem oil, clove oil, peppermint oil, cinnamon oil, thymeoil, oregano oil, garlic oil, anise oil, geranium oil, lime oil,lavender oil, components or derivatives thereof-including for examplegeraniol derived from geranium oil and eugenol derived from clove oil—ora combination of the foregoing. Table 1 presents a summary of majorchemical constituents (i.e. components) of some pesticidal natural oils.In some embodiments, the pesticidal natural oil is any oil that includesone or more constituents common to two or more of the pesticidal naturaloils listed in Table 1 (i.e. neem oil, clove oil, peppermint oil,cinnamon oil, thyme oil, oregano oil, garlic oil, anise oil, geraniumoil, lime oil, lavender oil), including, but not limited to, thymol(found in oregano oil and thyme oil), p-cymene (found in oregano oil andthyme oil), 1,8-cineole (found in thyme oil and peppermint oil), eugenol(found in clove oil and cinnamon oil), limonene (found in cinnamon,peppermint, and lime oil), alpha-pinene (found in cinnamon oil, geraniumoil, and lime oil), carvacrol (found in oregano oil, thyme oil, andclove oil), gamma-terpinene (found in oregano oil and lime oil),geraniol (found in thyme oil and geranium oil), alpha-Terpineol (foundin thyme oil and anise oil), beta-caryophyllene (found in clove oil,cinnamon oil, and peppermint oil) and linalool (found in thyme oil,cinnamon oil and geranium oil, amongst others). In other embodiments,the pesticidal natural oil is any oil having as a constituent one of thefollowing compounds, or a combination of the following compounds:azadirachtin, nimbin, nimbinin, salannin, gedunin, geraniol, geranial,gamma-terpinene, alpha-terpineol, beta-caryophyllene, terpinen-4-ol,myrcenol-8, thuyanol-4, benzyl alcohol, cinnamaldehyde, cinnamylacetate, alpha-pinene, geranyl acetate, citronellol, citronellylformate, isomenthone, 10-epi-gamma-eudesmol,1,5-dimethyl-1-vinyl-4-hexenylbutyrate, 1,3,7-octatriene, eucalyptol,camphor, diallyl disulfide, methyl allyl trisulfide, 3-vinyl-4H-1,2dithiin, 3-vinyl-1,2 dithiole-5-cyclohexane, diallyl trisulfide,anethole, methyl chavicol, anisaldehyde, estragole, linalyl acetate,geranial, beta-pinene, thymol, carvacrol, p-cymene, beta-myrcene,alpha-myrcene, 1,8-cineole, eugenol, limonene, alpha-pinene, menthol,menthone, and linalool.

TABLE 1 Chemical Constituents of Pesticidal Natural Oils Essential oilChemical Constituent Reference Oregano oil Thymol; Carvacrol; p- Vokou;Toncer cymene; gamma- terpinene; alpha- terpinene; linalool Neem oilAzadirachtin; Nimbin; Schmutterer Nimbinin; Salannin; Gedunin Thyme oilThymol; Geraniol; Thompson; Granger & Carvacrol; Linalool; Passet;Shabnum & Wagay alpha-Terpineol; p- Cymene; 1,8-Cineole; terpinen-4-ol;Myrcenol- 8; Thuyanol-4; mycrene; gamma-terpinene; alpha- terpineneClove oil Eugenol; benzyl alcohol; Chaieb carvacrol; thymol;cinnamaldehyde; beta- caryophyllene Cinnamon oil Linalool; cinnamylKaul; Simic acetate; beta- caryophyllene; alpha- pinene; eugenol;cinnamaldehyde; limonene Geranium oil Geraniol; linalool; geranylRajeswara Rao acetate; citronellol; citronellyl formate; isomenthone;alpha- pinene; 10-epi-gamma- eudesmol Peppermint oil Menthol; Menthone;1,8- Gochev; Clark & Menary Cineole; Methyl acetate; Limonene; beta-caryophyllene Lavender oil 1,5-Dimethyl-1-vinyl-4- Hui; Shellie,Mondello, hexenylbutyrate; 1,3,7- Marriott, & Dugo Octatriene;eucalyptol; camphor Garlic oil Diallyl disulfide; Methyl Kimbaris; Avatoallyl trisulfide; 3-Vinyl- 4H-1,2 dithiin; 3-Vinyl- 1,2 dithiole-5-cyclohexane; Diallyl trisulfide Anise oil Anethole; methyl Santos;Arslan chavicol; anisaldehyde; estragole; alpha- Terpineol; linaloolLime oil d-limonene; linalyl Vasudeva & Sharma; acetate; beta-myrcene;Lota, M.-L. linalool; alpha-pinene; geranial; beta-pinene;gamma-terpinene

Table 2 presents a summary of known pesticidal activities (includinginsecticidal, acaricidal, ovicidal, larvicidal, reducing growth rate,and pupation inhibiting activities) of constituents of some pesticidalnatural oils. In some embodiments, the pesticidal natural oil is any oilor any constituent that comprises a significant quantity (i.e. an amountof the constituent sufficient to provide the natural oil with pesticidalactivity) of one or more constituents possessing insecticidal activity.In some embodiments, the pesticidal natural oil is any oil thatcomprises a significant quantity (i.e. an amount of the constituentsufficient to provide the natural oil with pesticidal activity) of oneor more of the constituents listed in Table 2, namely thymol, p-cymene,eugenol, cinnamaldehyde, linalool, cinnamyl acetate, menthol,d-limonene, anethole, carvacrol, alpha-pinene, geraniol, 1,8-cineole,myrcene, anisaldehyde, alpha-terpineol, alpha-terpinene,gamma-terpinene, terpinen-4-ol, and beta-myrcene. In some embodiments,the constituent known to possess insecticidal activity is a terpene, forexample, azadirachtin. In some embodiments, the constituent of thepesticidal natural oil is present in an amount greater than or equal toabout 0.1%, greater than or equal to about 0.5% or greater than or equalto about 1% by weight in the pesticidal natural oil.

TABLE 2 Known Pesticidal Activities of Chemical Constituents ofPesticidal Natural Oils Compound Activity Reference Thymol Insecticidalactivity - Lee M. domestica & S. litura Thymol Insecticidal activity -Franzios D. melanogaster Thymol Insecticidal activity - Traboulsi C.pipiens molestus p-Cymene Antifeedant activity - Salom pales weevilEugenol Antifeedant activity - Jones & Firn P. Brassicae larvae EugenolInsecticidal activity - Yang et al. (2003) P. capitis EugenolInsecticidal activity - Trongtokit A. dirus mosquitoes EugenolAcaricidal activity - Kim, Kim, & Ahn D. farina & D. pteronyssinusCinnamaldehyde Insecticidal activity - Samarasekera C. quinquefasciatus& A. tessellatus Cinnamaldehyde Acaricidal activity - Chang & Chengtermites Linalool Insecticidal activity - Yang et al. (2005) P. humanuscapitis Linalool Acaricidal activity - Perrucci P. cuniculi LinaloolAntifeedant activity - Hummelbrunner, & Isman S. litura Linalool Reducegrowth rate - Karr & Coats B. germanica Cinnamyl acetate Insecticidalactivity - Yang et al. (2005) P. humanus capitis Menthol Insecticidalactivity - Ellis & Baxendale Tracheal mites Menthol Inhibit pupation -Harwood, Modenke, & Berry P. saucia Menthol Insecticidal activity -Tripathi T. castaneum & C. maculatus d-limonene Insecticidal activity -Lee (1997); Don-Pedro M. domestica, D. virgifera, S. litura, somecockroaches d-limonene Reduce growth rate - Karr & Coats B. germanicaAnethole Insecticidal activity - Chang & Ahn B. germanica AnetholeInsecticidal activity - Fuhremann, et al. house fly CarvacrolInsecticidal activity - Hierro, et al. (2004) A. simplex CarvacrolInsecticidal activity - Traboulsi C. pipiens molestus alpha-pineneInsecticidal activity - Traboulsi C. pipiens molestus GeraniolInsecticidal activity - Hierro A. simplex 1,8-Cineole Acaricidalactivity - Miresmailli, Bradbury & house dust mites Isman 1,8-CineoleReduce growth rate - Obeng-Ofori & Reichmuth Coleopteran sp. 1,8-CineoleInsecticidal activity - Tripathi, Prajanpati, T. castaneum Aggarwal, &Kumar Myrcene Reduce growth rate - Karr & Coats B. germanicaAnisaldehyde Insecticidal activity - Marcus & Lichtenstein house flyalpha-Terpineol Reduce growth rate - Karr & Coats B. germanicaalpha-Terpineol Antifeedant activity - Hummelbrunner & Isman S. lituraalpha-Terpinene Larvicidal activity - Cheng (2009) A. aegypti & A.albopictus gamma-terpinene Larvicidal activity - Cheng (2009) A. aegypti& A. albopictus gamma-terpinene Larvicidal activity - Abbassy A. fabae &S. littoralis Terpinen-4-ol Larvicidal activity - Abbassy A. fabae & S.littoralis p-cymene Larvicidal activity - Cheng (2009) A. aegypti & A.albopictus beta-myrcene Larvicidal activity - Cheng (2009) A. aegypti &A. albopictus

Other oils that can be used, alone or in combination, as additives insome embodiments of the present invention can be derived from plant,animal or mineral sources, or be synthetic. Such oils may be added as acarrier and/or for various other purposes, including but not limited to,improving odor characteristics (e.g. acting as an odor-masking agent),improving properties of another oil used as an active ingredient,decreasing repellency, acting as a pesticide, and/or improving otherproperties of the formulation. Such oils include, but are not limitedto, castor oil, orange oil, citrus oil, cedar oil, linseed oil, soybeanoil, licorice oil, mint oil, sweet birch oil, canola oil, jojoba oil,lavandin oil, mustard seed oil, coconut oil, eue oil, tulsi oil, almondoil, cottonseed oil, corn oil, germanium oil, sesame oil, tung oil,rosemary oil, basil oil, fennel oil, ginger oil, grapefruit oil,mandarin oil, pepper oil, rose oil, tangerine oil, tea tree oil, teaseed oil, pine oil, cardamom oil, cassia oil, celery oil, cognac oil,dill weed oil, juniper oil, guiacwood oil, parsley oil, pimento leafoil, apricot oil, origanum oil, betel leaf oil, ajowan oil, chilly seedoil, cubeb oil, curry oil, frankincense oil, ginger grass oil, heengoil, jamrosa oil, kalaunji oil, citronella oil, linaloe berry oil, bantulasi oil, bursera oil, lemon balm oil, karanja oil, nepetalactone oil,mink oil, limba pine oil, litsea cubeba oil, lovage oil, manuca oil,marjoran oil, milfoil oil, myrrh oil, myrtle oil, neroli oil, niaulioil, cumin seed oil, cyperiol oil, gereniol oil, grape seed oil, hinokioil, laurel berry oil, lichen oil, mace oil, mango ginger oil, menthapipereta oil, paprika oil, vetivert oil, wheat germ oil, macassar oil,mentha citreta oil, musk melon oil, nar kachur oil, palmarosa oil,patchouli oil, pomegranate oil, pumpkin oil, tomar seed oil, canangaoil, avocado oil, safflower oil, abies alba needle oil, ambrette seedoil, amyris oil angelica root oil, artemisia oil, estragon oil, firneedle oil, galangal oil, galbanum oil, olibanum oil, palmarosa oil,patchouli oil, birch oil, cajeput oil calamus oil, cedarwood oil,wintergreen oil, carrot oil, costus oil, cypress oil, davana oil, dwarfpine needle oil, elemi oil, guajac oil, hop oil, hyssop oil, chamomileoil, jasmine oil, larch oil, rosewood oil, oil, sassafras oil, tagetesoil, thuja oil, valerian oil, verbena oil, vervain oil, vetiver oil,wormwood oil, ylang ylang oil, olive oil, evening primrose oil, hazelnutoil, grape core oil, peach core oil, walnut oil, sunflower oil,sandalwood oil, turmeric oil, nutmeg oil, soy oil, vegetable oils,menthol oil, eucalyptol, camphor oil, cedar leaf oil, laurel leaf oil,balsam oil, bay oil, capsicum oil, spearmint oil, caraway seed oil,lemon eucalyptus oil, lemongrass oil, sage oil, pennyroyal oil, bergamotoil, mineral oil, other natural or essential oils, or combinationsthereof.

In some embodiments, the additive is an odor-masking agent or compound.In some embodiments, the odor-masking agent is vanilla extract,wintergreen oil, spearmint oil, clove oil, lemongrass oil, and/or acombination thereof.

In some embodiments, the additive can be a second pesticidal natural oilor other material having pesticidal activity, including for examplecinnamon oil, thyme oil, clove oil, clove leaf oil, clove bud oil,eugenol, lime oil, oregano oil, thyme oil, mint oil (including spearmintor peppermint oil), or the like.

In some embodiments, the additive can be an odor-neutralizing agent. Insome embodiments, the odor-neutralizing agent can be an odor-absorbentmaterial. In some embodiments, the additive is zeolite and/or othernatural or synthetic odor absorbent material.

Derivatives and/or components of neem oil that can be used inembodiments of the present invention include, but are not limited to,neem oil, palmitoleic acid, alpha-linolenic acid, stearic acid, palmiticacid, oleic acid, linoleic acid, campesterol, beta-sitosterol,stigmasterol, azadirachtin, meliantriol, melianone, gedunin,amoorastatin, vepinin, marrangin, vilasinin, nimbin, nimbolide,nimbolinin, ohchinolide, nimbolinin, salannin, meliacarpin, meliaquinal,nimbandiol, nimbinene, nimbocinone, kulactone, limocinol, limocinone,nimolinone, azadirachnol, or other triterpenoids, azadirone,azadiradione, azadirachtol, epoxyazadiradione, other compounds derivedfrom neem, related to neem, combinations thereof, and their activederivatives.

Derivatives and/or components of other pesticidal natural oils that canbe used in some embodiments of the present invention include, but arenot limited to, thymol, p-cymene, 1,8-cineole, eugenol, limonene,carvacrol, menthol, alpha-pinene, linalool, menthone, carvacrol,gamma-terpinene, geraniol, alpha-terpineol, beta-caryophyllene,linalool, gedunin, geranial, terpinen-4-ol, myrcenol-8, thuyanol-4,benzyl alcohol, cinnamaldehyde, cinnamyl acetate, geranyl acetate,citronellol, citronellyl formate, isomenthone, 10-epi-gamma-eudesmol,1,5-dimethyl-1-vinyl-4-hexenylbutyrate, 1,3,7-octatriene, eucalyptol,camphor, diallyl disulfide, methyl allyl trisulfide, 3-vinyl-4H-1,2dithiin, 3-vinyl-1,2 dithiole-5-cyclohexane, diallyl trisulfide,anethole, methyl chavicol, anisaldehyde, estragole, linalyl acetate,beta-pinene, beta-myrcene, alpha-myrcene, menthol, and other compoundsderived from pesticidal natural oils, combinations thereof, and theiractive derivatives.

In some embodiments, a surfactant is used in preparing pesticidalcompositions or pest control agents. Suitable surfactants can beselected by one skilled in the art. Examples of surfactants that can beused in some embodiments of the present invention include, but are notlimited to, ethoxylated castor oil, sodium lauryl sulfate, saponin,ethoxylated alcohols, ethoxylated fatty esters, alkoxylated glycols,ethoxylated fatty acids, carboxylated alcohols, carboxylic acids, fattyacids, ethoxlylated alkylphenols, fatty esters, sodium dodecylsulfide,other fatty acid-based surfactants, other natural or syntheticsurfactants, and combinations thereof. In some embodiments, thesurfactant(s) are non-ionic surfactants. In some embodiments, thesurfactant(s) are ionic surfactants. The selection of an appropriatesurfactant depends upon the relevant applications and conditions of use,and appropriate surfactants are known to those skilled in the art.

In some embodiments, a pesticidal composition includes a suitablecarrier. A suitable carrier can be selected by one skilled in the art,depending on the particular application desired and the conditions ofuse of the composition. Commonly used carriers include ethanol,isopropanol, other alcohols, water and other inert carriers listed bythe EPA as a Minimal Risk Inert Pesticide Ingredients (4A), InertPesticide Ingredients (4B) or under EPA regulation 40 CFR 180.950, eachof which is hereby incorporated herein in its entirety for all purposesincluding for example, citric acid, lactic acid, glycerol, castor oil,benzoic acid, carbonic acid, ethoxylated alcohols, ethoxylated amides,glycerides, benzene, butanol, I-propanol, hexanol, other alcohols,dimethyl ether, and polyethylene glycol.

Some embodiments of the present invention include combinations of apesticidal natural oil (and/or components and/or derivatives thereof)with a polar aromatic solvent and one or more other natural oils (plant,animal or mineral derived), synthetic oils, and/or chemical derivativesof any of the foregoing.

In some embodiments, a pesticidal composition comprises a pesticidalnatural oil at a concentration of between 0.25% and 99.3% by weight,including any concentration therebetween e.g. 0.3%, 0.4%, 0.5%, 0.6%,0.7%, 0.8%, 0.9%, 1%, 2%, 5%, 7.5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%,45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 98% or 99% byweight; and a polar aromatic solvent at a concentration between 0.7% and99.75% by weight, including any concentration therebetween e.g. 0.8%,0.9%, 1.0%, 1.2%, 1.4%, 1.6%, 1.8%, 2%, 3%, 4%, 5%, 7.5%, 10%, 15%, 20%,25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%,95%, 98% or 99% by weight. In some embodiments, the polar aromaticsolvent is present at a concentration between 0.13 mol/kg and 8.3 mol/kgor any value therebetween, e.g. 0.2, 0.4, 0.6, 0.8, 1.0, 1.5, 2.0, 2.5,3.0, 3.5, 4.0, 4.5, 5.0, 5.5, 6.0, 6.5, 7.0, 7.5, or 8.0 mol/kg.

In some embodiments, a pesticidal composition is provided in which theweight ratio of polar aromatic solvent to pesticidal natural oil is inthe range of 1.5:1 to 7:1, or any range therebetween including e.g. 2:1,2.5:1, 3:1, 4:1, 5:1, or 6:1.

One exemplary composition according to one embodiment includes neem oilor a component or derivative thereof, acetophenone or another polararomatic solvent, and optionally includes a surfactant, additionalinsect controlling compounds and/or additional natural oils or otherproducts to add fragrance, decrease repellency, or extend the range ofinsects susceptible to the composition. In one embodiment, such acomposition includes neem oil (or a derivative thereof) at aconcentration between 0.1% and 99% by weight, including anyconcentration therebetween e.g. 0.2%, 0.25%, 0.3%, 0.4%, 0.5%, 0.6%,0.7%, 0.8%, 0.9%, 1%, 2%, 5%, 7.5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%,45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 98% or 99% byweight; and acetophenone at a concentration between 0.7% and 99.75% byweight (between 0.13 mol/kg and 8.3 mol/kg or any value therebetween,e.g. 0.2, 0.4, 0.6, 0.8, 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, 5.0,5.5, 6.0, 6.5, 7.0, 7.5, or 8.0 mol/kg), including any concentrationtherebetween e.g. 0.8%, 0.9%, 1.0%, 1.2%, 1.4%, 1.6%, 1.8%, 2%, 3%, 4%,5%, 7.5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%,70%, 75%, 80%, 85%, 90%, 95%, 98% or 99% by weight. The exemplarycomposition optionally includes one or more surfactants, otherpesticidal ingredients, stabilizers, carriers, diluents, or othernon-pesticidal ingredients, and/or other natural oils.

In one exemplary embodiment, a pesticidal composition includes acombination of neem oil at a concentration of 5.5% by weight,acetophenone at a concentration of 15.5% by weight, natural oils(lemongrass oil, spearmint oil, clove oil, and wintergreen oil) at 8% or3.4% by weight and a surfactant at a concentration of 5.0% by weight. Inone exemplary embodiment, a pesticidal composition includes acombination of neem oil at a concentration of 5.5% by weight,acetophenone at a concentration of 18.25% by weight, and 1.25%ethoxylated castor oil by weight.

Exemplary formulations according to one exemplary embodiment comprisingneem oil as the pesticidal natural oil and acetophenone as the solventwere shown to demonstrate improved dry residue pesticidal activity ascompared with neem oil alone when neem oil and acetophenone are presentat a concentration of at least 0.55% and 1.55% by weight, respectively.

Formulations according to another exemplary embodiment were found todemonstrate improved dry residue prevention of egg eclosion as comparedwith neem oil alone when neem oil and acetophenone were present atconcentrations of at least 0.25% and 0.7% by weight, respectively.

Some embodiments of the present invention can be used to control pestssuch as arthropods, including insects and arachnids. Exemplaryembodiments of the present invention have been demonstrated to haveefficacy against arthropods including insects, spiders, centipedes andmillipedes, including bed bugs, German cockroaches (Blatlellagermanica), Smoky Brown cockroaches (Periplaneta fuliginosa), Americancockroaches (Periplaneta americana), cat fleas (Ctenocephalides felis),fire ants (Solenopsis Invicta), black carpenter ants (Camponotuspennsylvanicum), pavement ants (Tetramorium caespitum), field ants(Formica sp.), moisture ants (Lasius sp.), wood ants (Formica rufa),house flies (Musca domestica), bottle flies (Lucilia sericata), giantsilverfish (Ctenolepisma longicaudata), firebrats (Thermobia domestica),bean aphids (Aphis fabae), pea aphids (Acyrthosiphon pisum), termites(Reticulitermes flavipes), granary weevils (Sitophilus granarius), maizeweevils (Silophilus zeamais), confused flour beetles (Triboliumconfusum), rusty grain beetles (Cryptolestes ferrugineus), dust mites(Dermatophagoides farinae), millipedes (Cylindroiulus caeruleocinctus),centipedes (Strigamia aluminata), sowbugs (Oniscus asellus), orabatidmites (Haplozetes sp.), house crickets (Acheta domestica), black widowspiders (Latrodectus mactans), brown recluse spiders (Loxoscelesreclusa), and pharaoh ants (Monomorium pharaonis). Exemplary embodimentsof the present invention have been demonstrated to have efficacy inpreventing eclosion of arthropod eggs, including bed bug eggs andcockroach eggs. Some embodiments of the present invention can also beused to control insects, arachnids, centipedes, millipedes, or otherarthropods upon which they are expected to be effective based on theirdemonstrated activity, including, but not limited to, whiteflies,mosquitoes, other species of flies, other species of aphids, otherspecies of silverfish, lice, stink bugs, moths, beetles, lace bugs,whiteflies, green peach aphids, western floral thrips, diamondbackmoths, leafminers, grasshoppers, crickets, locusts, leafhoppers,planthoppers, psyllids, scale insects, midges, fruit flies, earworms,bollworms, armyworms, budworms, hornworms, milkweed bugs, mealy bugs,weevils, botflies, face flies, sawflies, rice bugs, coffee bugs,vegetable bugs, corn borers, horn flies, blowflies, sowbugs, pillbugs,mites, centipedes and millipedes. Exemplary embodiments of the presentinvention have been demonstrated to have efficacy against arachnidsincluding cellar spiders, ticks, black widow spiders and brown reclusespiders. Some embodiments of the present invention can also be used tocontrol other arachnids upon which they are expected to be effective,including, but not limited to, scorpions and other species of spiders.This disclosure is intended to encompass uses against all of the above,as well as uses against other pests, including other insects andarachnids, and other organisms including fungi, bacteria, viruses, andnematodes.

In some embodiments, the pesticidal compositions described herein areeffective to kill and/or control pests and/or prevent or reduceoviposition and/or prevent or reduce eclosion of their eggs. In someembodiments, the pesticidal compositions described herein exhibiteffective knockdown pesticidal activity, exhibit effective dry residuepesticidal activity, and/or exhibit effective prolonged residualpesticidal activity.

In some embodiments, the pesticidal compositions described herein areeffective to kill and/or control pests and/or prevent oviposition and/orprevent eclosion of their eggs, or exhibit improved knockdown of a pest,dry residue pesticidal activity, and/or prolonged residual pesticidalactivity, when the concentration of each of the pesticidal natural oiland the polar aromatic solvent is below a level at which the pesticidalnatural oil and the polar aromatic solvent used alone would be effectiveto achieve the same function. In some embodiments, the pesticidalcompositions described herein exhibit a synergistic pesticidal effect ascompared with the activity the pesticidal natural oil or the polararomatic solvent used alone. In some embodiments, the pesticidalcompositions described herein exhibit significantly improved pesticidaleffect as compared with the activity of the pesticidal natural oil orthe polar aromatic solvent used alone at the same concentration.

Some embodiments of the present invention can be used to control peststhat affect humans and non-human mammals including bed bugs,cockroaches, lice, fleas, ticks, mites, and scabies. Some embodiments ofthe present invention can be used to control pests that affect plants oragriculture, such as aphids or nematodes. In some embodiments, any ofthe compositions described above may be used in any situation in which aneem oil-based insect control agent is currently employed.

In some embodiments, any of the compositions described above areformulated in a deliverable form suited to a particular application.Deliverable forms that can be used in accordance with embodiments of thepresent invention include, but are not limited to, liquids, emulsions,solids, waxes, dusts, fumigants, aqueous suspensions, oily dispersions,pastes, powders, dusts, emulsifiable concentrates, aerosol sprays, woodfillers, varnishes, wood treatments or furniture oils, detergents,drywall mixtures, fumigating candles, caulking compositions, crack andcrevice fillers, sealing agents, and mattress and mattress covertreatments. Suitable deliverable forms can be selected and formulated bythose skilled in the art using methods currently known in the art.

Some embodiments of the present invention demonstrate effective insectcontrol activity on surfaces where pest products are commonly employed,including, but not limited to, carpet, mattresses, wood, and fabrics. Insome embodiments, any of the compositions described above are applied tosurfaces inside a household, residence or building. In some embodiments,any of the compositions described above are applied to mattresses,sheets, fabrics, travel bags/suitcases, carpets, painted or unpaintedhard surfaces, wood, flooring, furniture and/or buildings. In someembodiments, any of the compositions described herein are appliedoutdoors or to plants or agricultural areas and/or inside or outsidestructures.

Some embodiments are effective as an insect control agent againstinsects resistant to pyrethrins (eg. pyrethrum) and pyrethroids (eg.deltamethrin, bifenthrin, λ-cyhalothrin, etc.). In some embodiments, thepyrethrin-resistant insect is a bed bug (Cimex lectularius L.).

Some embodiments provide methods of using any of the compositionsdescribed above to control populations of bed bugs and/or other insects,arachnids and/or other arthropods. Some embodiments provide a method ofkilling and/or controlling pests and/or preventing oviposition and/oreclosion of their eggs by applying any of the compositions describedherein directly to the pests or to surfaces where the pests or theireggs may contact the composition. Some embodiments provide a method ofkilling and/or controlling pests and/or preventing oviposition and/oreclosion of their eggs by applying any of the compositions describedherein to surfaces so that the pests and/or their eggs will be exposedto the compositions, including to vapors of the compositions. In someembodiments, the pests are insects and/or arachnids and/or centipedesand/or millipedes. In some embodiments, the insects are of the ordersHemiptera, Hymenoptera, Blattodea, Isoptera, Diptera, Lepidoptera,Thysanoptera, Thysanura, Coleopteran, Siphonaptera, Phthiraptera,Psocidae, Dermaptera, Orthoptera. In some embodiments, the pests are bedbugs or cockroaches.

In some embodiments, the methods of use of any of the compositionsdescribed herein include combination with natural oils for directapplication, dilution with an appropriate carrier for delivery as aready-to-use spray, or in a concentrated form to be diluted and applied.Other methods of use include, but are not limited to, use as a woodtreatment or furniture oil, as a laundry detergent, as a gel or pastewhich can be applied to a target location, as an oily emulsion, as adust formulation, as a component in drywall mixture, as a crack orcrevice filler or other sealing agent, as a foam, as a component incaulking compositions, as a fumigating mist or candle, as an aerosol oraerosol bomb, or in a formulation employed for treating mattresses ormattress covers. In some embodiments, any of the compositions describedabove are used for indoor domestic or commercial uses in dispersibleforms against a range of pests. Some embodiments of the presentinvention can be used in dispersible forms in agricultural or otheroutdoor settings to control pests.

In some embodiments, the compositions described herein exhibit prolongedresidual pesticidal activity, enabling a period of time to pass betweenre-treatment of target surfaces. In one embodiment, pests are killed orcontrolled, and/or oviposition and/or eclosion are prevented by applyingany of the compositions described herein directly to the pests or tosurfaces where the pests or their eggs may contact or otherwise beexposed to the composition. A period of time greater than about a week,e.g. 7 days, 8 days, 9 days, 10 days, 11 days, 12 days, 13 days, 14days, 15 days, 16 days, 17 days, 18 days, 19 days, 20 days, or 21 daysor longer is allowed to pass. Then any of the compositions describedherein are re-applied to the pests or to surfaces where the pests ortheir eggs may contact or otherwise be exposed to the composition.

Formulations according to some embodiments can be prepared in anysuitable manner. Some embodiments of the present invention providemethods for preparing pesticidal formulations comprising mixing apesticidal natural oil and/or a component and/or a derivative thereofand a polar aromatic solvent. In some embodiments, the pesticidalformulation is prepared by heating one or more pesticidal natural oils(or component or derivative thereof) in a water bath before any furthercomponents of the formulation are added. The surfactant is added to thepesticidal natural oil, and then one or more solvents are added to thepesticidal natural oil, allowing the solvent to solvate the oil beforeaddition of other ingredients. In some embodiments in which thepesticidal natural oil is neem oil, the formulation is prepared bywarming neem oil to a temperature of 25-30° C. before any furthercomponents of the formulation are added. The solvent is then added tothe oil, allowing the solvent to solvate the oil before addition ofother ingredients. Optionally, a surfactant and/or other ingredients(which may include additional natural oils or other pesticides) are thenadded. In some embodiments, a surfactant is added prior to addition ofthe solvent. Once all ingredients are completely solvated, they mayoptionally be combined with an appropriate amount of a conventionaldiluent and/or additional solvent (including different types ofsolvents). Other carriers, solvents, surfactants, pesticides, fragrancesor odor neutralizers may optionally be added. Appropriate preservativesor stabilizers may optionally be added. Materials that encapsulate,hold, transport, delay release or otherwise improve delivery mayoptionally be added.

EXAMPLES

Embodiments of the present invention are further described withreference to the following examples, which are intended to beillustrative and not limiting.

In the examples that follow, the neem oil used was cold pressed neemseed oil (“C.P. neem oil”).

Example 1—Dry Residue Pesticidal Activity

‘Solution A’ containing neem oil at 5.5% by weight, 15.5% acetophenoneby weight, 8% natural oils (lemongrass oil, spearmint oil, clove oil,and wintergreen oil) by weight, and 5.0% ethoxylated castor oil byweight was prepared with isopropyl alcohol (isopropanol) as a carrierdiluent. A serial dilution was performed, comprising 100% Solution A,50% Solution A in isopropanol, 25% Solution A in isopropanol, and 10%Solution A in isopropanol. 1.0 mL of each solution was applied to90-millimeter filter paper substrates in petri dishes. Substrates wereallowed to air dry for two hours, then were infested with adult bed bugs(approximately half male and half female). Replicates of each treatmentgroup and of a negative Control Group were tested concurrently.Mortality was observed at specified intervals after infestation. Adultbed bugs were counted dead if they were unresponsive when stimulated.

The percentage of dead adult bed bugs was measured at 1-, 2-, 4-, 8-,12-, 24-, 48-, 72-, and 480-hour intervals after infestation andcompared against controls. The data collected are summarized in Table 3.At levels as low as 0.55% neem oil and 1.55% acetophenone by weight thecombination demonstrated improved insecticidal activity over anuntreated control group. No insecticidal activity, relative to acontrol, was observed at concentrations of 0.055% neem oil and 0.155%acetophenone by weight.

TABLE 3 Dry Residue Pesticidal Activity. Control 100% 50% 25% 10% 1% %Concentration C.P. 0 5.5 2.75 1.375 0.55 0.055 Neem Oil (by weight) %Concentration 0 15.5 7.76 3.875 1.55 0.155 Acetophenone (by weight) Time(Hours) % Mortality 0 0.00 0.00 0.00 0.00 0.00 0.00 1 0.00 2.08 0.000.00 0.00 0.00 2 0.00 8.71 2.50 0.00 0.00 0.00 4 0.00 41.14 15.00 2.780.00 0.00 8 0.00 90.45 50.83 5.56 0.00 0.00 12 0.00 97.50 65.83 8.060.00 0.00 24 0.00 100.00 100.00 43.76 2.50 0.00 48 2.50 100.00 100.0073.41 5.00 0.00 72 2.50 100.00 100.00 85.68 14.77 0.00 480 16.82 100.00100.00 97.50 70.91 11.67

Example 2—Dry Residue Pesticide Activity of Various Pesticidal NaturalOils

This example illustrates the dry residual pesticidal activity offormulations containing a variety of pesticidal natural oils as activeingredients. Solutions were prepared by combining 2.5% by weight of thepesticidal natural oil as active ingredient, 2.5% by weight sodiumlauryl sulphate, 5.0% by weight solvent (either ethyl lactate oracetophenone as noted), and an appropriate amount of water as a diluent.1.0 mL of each solution was applied to three replicates of filter paper,90 millimetres in diameter, contained in petri dishes (Treated Groups).Treated Groups and three replicates of an untreated Control Group wereallowed to dry for two hours prior to infestation with a known number ofadult bed bugs (approximately half male and half female).

Bed bug mortality was assessed immediately after infestation and at 2-,4-, 8-, 12-, and 24-hour intervals after infestation, and dailythereafter until 33 days after infestation. Adult bed bugs were counteddead if they were unresponsive when stimulated. Table 4 summarizes theLT₅₀ (the mean point of time at which 50% of bed bugs had died), the 95%Confidence Interval (C.I.) and the maximum mortality observed for eachformulation.

TABLE 4 LT₅₀ and Maximum Mortality of Formulations IncorporatingPesticidal Natural Oils. Pesticidal LT₅₀ 95% C.I. Max Natural OilSolvent (hrs.) (hrs.) mortality Cinnamon Oil Acetophenone 3.06 2.77 to3.36 100% Cinnamon Oil Ethyl Lactate 14.00 13.16 to 15.05 100% Clove OilAcetophenone 5.25 4.90 to 5.59 100% Clove Oil Ethyl Lactate 10.58 10.03to 11.11 100% Eugenol Acetophenone 2.82 2.62 to 3.02 100% Eugenol EthylLactate 9.91 9.73 to 10.12 100% Oregano Oil Acetophenone 2.00Interrupted** 100% Oregano Oil Ethyl Lactate 9.53 9.32 to 9.74 100%Thyme Oil Acetophenone 3.10 2.89 to 3.31 100% Thyme Oil Ethyl Lactate17.24 16.65 to 17.82 100% Garlic Oil Acetophenone 11.98 10.86 to 13.09 90% Garlic Oil Ethyl Lactate 24.54 7.27 to 41.80 100% Anise OilAcetophenone 17.79 16.56 to 19.01 100% Anise Oil Ethyl Lactate 227.8N/A*  30% Geranium Oil Acetophenone 2.00 Interrupted** 100% Geranium OilEthyl Lactate 16.93 N/A*  90% Lime Oil Acetophenone 6.628 N/A*  89% LimeOil Ethyl Lactate 93.35 N/A*  45% Peppermint Oil Acetophenone 2.18 2.15to 2.22 100% Peppermint Oil Ethyl Lactate N/A* N/A*  55% Lavender OilAcetophenone 3.57 3.01 to 4.14 100% Lavender Oil Ethyl Lactate N/A* N/A* 40% Neem Oil Acetophenone 6.54 6.07 to 7.02 100% Neem Oil Ethyl LactateN/A* N/A*  40% Control None N/A* N/A*  30% *N/A: LT₅₀ and 95% C.I.cannot be reliably calculated for formulations that do not reach 100%maximum mortality **Interrupted: 95% C.I. cannot be reliably calculatedwhen the LT₅₀ is below two hours

Example 3—Dry Residual Insecticidal Activity of Various Solvents

This example illustrates the dry residual pesticidal activity offormulations including neem oil and various organic solvents includingalcohols, ketones, esters and carboxylic acids. Solutions were preparedusing 5.5% by weight neem oil; the percent by weight of organic solventindicated in Table 5 and an appropriate amount of isopropanol as acarrier diluent. The percent by weight of each solvent was varied toensure a consistent molar quantity of solvent in each solution (finalconcentration of 1.5 mol/kg). Treated Groups for each solution wereprepared by treating filter paper, 90 mm in diameter, with 1.0 mL ofsolution and allowing it to air dry for four hours. A known number ofadults were added to each treated dish, four hours after treatment. Bedbug mortality was assessed immediately after infestation and at 1-hour,2-hour, 4-hour, 6-hour, 8-hour, 10-hour, 12-hour, and 24-hour intervals,and at 24-hour intervals thereafter until 14 days after infestation.Adult bed bugs were counted dead if they were unresponsive whenstimulated. Table 5 shows the maximum % mortality of all treated groupsand the time taken to reach maximum mortality.

A number of the tested organic solvents, from the classes of alcohols,ketones, esters and carboxylic acids, proved effective in combinationwith neem oil. Solvents that included at least one aryl group weregenerally more effective than solvents that contained only alkyl groups.Alkyl aryl ketones were consistently effective solvents, and small arylalcohols, aryl alkyl alcohols, aryl ketones, and alkyl aryl esters alsoproved effective in combination with neem oil.

TABLE 5 Maximum % Mortality of Formulations with Differing OrganicSolvents. Time to Class of % Solvent Max. Max Solvent Formula (w/w)Compound name Mortality Mortality Alcohol X = CH(OH) Alkyl Alk-X—Halcohols Alk = butyl 11.26 1-Butanol  40% 8 d Alk = hexyl 15.521-Hexanol  40% 14 d Alk = ethyl-pentyl 19.78 2-Ethyl-1-hexanol 100% 72hr (Branched alkyl) Alk = decyl 24.04 1-Decanol 100% 11 d IsoalcoholsAlk₁-X-Alk₂ Alk₁ = methyl 93.25 2-Propanol (IPA)  40% 6 d Alk₂ = methylAlk₁ = ethyl 11.26 2-Butanol  20% 14 d Alk₂ = methyl Cyclohexanol 15.21Cyclohexanol  60% 14 d Aryl alcohol Ar—X—H Ar = phenyl 16.42 Benzylalcohol 100% 24 hr Aryl-alkyl Ar—X-Alk alcohol Ar = phenyl 18.561-Phenylethanol 100% 24 hr Alk = methyl Aldehyde and Ketone X = (C═O)Aldehyde Ar—X—H Ar = phenyl 16.12 Benzaldehyde 100% 14 d Alkyl-AlkylAlk₁-X-Alk₂ ketone Alk₁ = methyl 19.17 Methylcyclohexylketone  70% 11 dAlk₂ = cyclohexyl Cyclohexanone 14.91 Cyclohexanone  50% 10 d Aryl-AlkylAr—X-Alk ketone Ar = phenyl 18.25 Acetophenone 100% 24 hr Alk = methylAr = 4-methylphenyl 20.38 4′-Methylacetophenone 100% 48 hr Alk = methylAr = 2,4- 22.51 2′,4′-Dimethylacetophenone 100% 24 hr dimethylphenyl Alk= methyl Ar = 3,4- 22.51 3′,4′-Dimethylacetophenone 100% 48 hrdimethylphenyl Alk = methyl Ar = phenyl 20.69 Propiophenone 100% 24 hrAlk = ethyl Ar = 4-methylphenyl 22.51 4′-Methylpropiophenone 100% 24 hrAlk = ethyl Ar = phenyl 22.51 Butyrophenone 100% 24 hr Alk = propyl Ar =phenyl 22.51 Isobutyrophenone 100% 48 hr Alk = isopropyl Ar = phenyl24.64 Valerophenone 100% 24 hr Alk = butyl Ar = phenyl 26.77Hexanophenone 100% 6 d Alk = pentyl Aryl-aryl Ar₁—X—Ar₂ ketone Ar₁ =2,4- 37.4 2,2′-4,4′ 100% 24 hr dihydroxyphenyl TetrahydroxybenzophenoneAr₂ = 2,4- dihydroxyphenyl Carboxylic Acids and Esters X = (C═O)—OAlkyl-alkyl Alk₁-X-Alk₂ ester Alk₁ = methyl 13.38 Ethyl acetate  30% 14d Alk₂ = ethyl Alk₁ = methyl 30.12 2-tert-Butylcyclohexylacetate 100% 96hr Alk₂ = 2-tert- butylcyclohexyl Aryl acid Ar—X—H Ar = phenyl 18.55Benzoic acid 100% 48 hr Aryl-alkyl Ar—X-Alk ester Ar = 4-hydroxyphenyl27.27 Propyl-4-hydroxybenzoate 100% 24 hr Alk = propyl

Example 4—Dry Residual Insecticidal Activity of Various Solvents

This example illustrates the dry residual pesticidal activity offormulations including neem oil and various organic solvents includingalcohols, ketones, esters and carboxylic acids. Solutions were preparedusing 5.5% by weight neem oil; 1.5 mol/kg organic solvent; and anappropriate amount of isopropanol as a carrier diluent. The percent byweight of each solvent was varied to ensure a consistent molar quantityof solvent in each solution. Treated Groups for each solution wereprepared by treating filter paper, 90 mm in diameter, with 1.0 mL ofsolution and allowing it to air dry for four hours in ahighly-ventilated room. A known number of adults were added to eachtreated dish, four hours after treatment. Bed bug mortality was assessedimmediately after infestation and at 1-hour, 2-hour, 4-hour, 6-hour,8-hour, 10-hour, 12-hour, and 24-hour intervals, and at 24-hourintervals thereafter until 14 days after infestation. Adult bed bugswere counted dead if they were unresponsive when stimulated. Table 6shows the maximum % mortality of all treated groups and the time takento reach maximum mortality.

A number of the tested organic solvents, from the classes of alcohols,ketones, esters, ethers, aldehydes and carboxylic acids, provedeffective in combination with neem oil. Solvents that included at leastone aryl group were generally more effective than solvents thatcontained only alkyl groups.

TABLE 6 Maximum % Mortality of Formulations with Differing OrganicSolvents. Time to Max. Max Class Formula and ID Compound name MortalityMortality Alcohol X = CH(OH) Alkyl alcohol Alk-X—H Alk = nonyl 1-Nonanol100% 48 hr Alk = butyl-heptyl 2-Butyl-1-octanol 100% 8 d (Branchedalkyl) Alk = dodecyl 1-dodecanol  90% 14 d Alk = hexyl-nonyl2-hexyl-1-decanol 100% 14 d (Branched alkyl) Isoalcohol Alk₁-X-Alk₂ Alk₁= butyl 3-Heptanol  30% 14 d Alk₂ = ethyl Alk₁ = hexyl 2-Octanol 100% 48hr Alk₂ = methyl Alk₁ = isobutyl 2,6-Dimethyl-4-heptanol  20% 14 d Alk₂= isobutyl Aryl alcohol Ar—X—H Ar = 3,4-dimethylphenyl3,4-dimethylbenzyl alcohol 100% 14 d Aryl-alkyl Ar—X-Alk alcohol Ar =4-methylphenyl Alpha-4-dimethylbenzyl alcohol 100% 24 hr Alk = methyl Ar= phenyl 2-Phenyl-2-propanol 100% 24 hr Alk = dimethyl Aldehyde andKetone X = (C═O) Aryl-Aldehyde Ar—X—H Ar = 4-methylphenyl p-Tolualdehyde 50% 6 d Ar = 2-hydroxy-5- 2-hydroxy-5-methyl benzaldehyde 100% 24 hrmethylphenyl Aryl-Alkyl Ar—X-Alk ketone Ar = 4-hydroxyphenyl4′-Hydroxyacetophenone  50% 9 d Alk = methyl Ar = 2-hydroxyphenyl2′-Hydroxyacetophenone 100% 24 hr Alk = methyl Ar = 4-hydroxyphenyl4′-Hydroxyvalerophenone  70% 14 d Alk = butyl Ar-phenyl Cyclohexylphenyl ketone  90% 8 d Alk = cyclohexyl Carboxylic Acids and Esters X =(C═O)—O Aryl acid Ar—X—H Ar = 4-hydroxyphenyl 4-Hydroxy benzoic acid100% 24 hr Ar = 4-hydroxy-3- 4-Hydroxy-3-methyl benzoic acid  60% 14 dmethylphenyl Aryl-alkyl Ar—X-Alk ester Ar = phenyl Ethyl benzoate 100%48 hr Alk = ethyl Ar = phenyl Isobutyl benzoate  90% 8 d Alk = isobutylAryl-aryl ester Ar—X—Ar Ar = phenyl Benzyl benzoate 100% 8 d Alk =benzyl Phenol and Ethers X = O Ar—X—H Phenol 100% 24 hr Aryl-AlkylAr—X-Alk ether Ar = benzyl Benzyl methyl ether  60% 8 d Alk = methyl Ar= phenyl Butyl phenyl ether 100% 6 d Alk = butyl Ar =4-(1-propenyl)benzyl Trans-anethole 100% 5 d * Alk = methyl Aryl-ArylAr—X—Ar ether Ar₁ = benzyl Dibenzyl ether  90% 7 d Ar₂ = benzyl Ar₁ =phenyl Diphenyl ether 100% 72 hr Ar₂ = phenyl Benzenes Benzene  40% 14 dToluene  50% 14 d p-Xylene  30% 14 d * Solvent tested in separate studyfrom other solvents in table (under same experimental conditions)

Example 5—Dry Residual Insecticidal Activity

Three solutions were prepared, each containing isopropanol as a carrierdiluent: ‘Solution A’ included 5.5% neem oil and 1.25% castor oil byweight; ‘Solution B’ included 18.25% acetophenone and 1.25% castor oilby weight; and ‘Solution C’ included 5.5% neem oil, 18.25% acetophenone,and 1.25% castor oil by weight. 1.0 mL of each solution was applied toone replicate of filter paper, 90 millimetres in diameter, contained inpetri dishes (Treated Groups). An untreated Control Group was testedconcurrently. All Treated Groups were allowed to dry for four hoursprior to infestation with adult bed bugs.

Bed bug mortality was assessed immediately after infestation and at 2-,4-, 8-, 10-, and 24-hour intervals after infestation. Adult bed bugswere counted dead if they were unresponsive when stimulated. Table 7summarizes the mean mortality data of all formulations at the statedobservation intervals.

Solution C demonstrated significantly higher pesticidal activity at allobserved intervals, than a solution of acetophenone alone (Solution B)or neem oil alone (Solution A).

TABLE 7 Mean % Mortality of 4-Hour Dry Residues. 10 24 0 HR 2 HR 4 HR 8HR HR HR Control No Treatment 0% 0% 0% 0% 0% 0% Solution A 5.5% Neem Oil0% 0% 0% 0% 0% 9% Solution B 18.25% 0% 0% 0% 0% 10% 70% AcetophenoneSolution C 5.5% Neem Oil + 0% 30% 40% 60% 70% 90% 18.25% Acetophenone

Example 6—Dry Residual Insecticidal Activity

Six solutions were prepared, each containing isopropanol as a carrierdiluent: ‘Solution A’ included 5.5% neem oil by weight, 15.5%acetophenone by weight, 1.8% natural oils (lemongrass oil andwintergreen oil) by weight and 1.25% surfactant by weight; ‘Solution B’included 5.5% neem oil by weight, 15.5% acetophenone by weight, and 5.0%surfactant by weight; ‘Solution C’ included 5.5% neem oil alone byweight; ‘Solution D’ included 15.5% acetophenone alone by weight;‘Solution E’ included 1.8% natural oils (lemongrass oil and wintergreenoil) by weight; and ‘Solution F’ included 5.5% neem oil by weight and15.5% acetophenone by weight. 1.0 mL of each solution was applied tofilter paper, 90 millimetres in diameter, contained in petri dishes (theTreated Groups). The surfactant used in all solutions was ethoxylatedcastor oil. Two replicates for each Treated Group and two replicates ofa negative Control Group were tested concurrently. Treated surfaces weresealed in petri dishes with a plastic paraffin film and allowed to sitfor eight days, then were exposed to the air for four hours, prior toinfestation with a known number of adult bed bugs.

Immediately after infestation and at 4-, 8-, 12-, 24-, 48-, 72-, 96-,120-, and 144-hour intervals after infestation, the number of bed bugskilled in the intervening period was assessed. Adult bed bugs werecounted dead if they were unresponsive when stimulated. The meanpercentage of dead adult bed bugs was calculated for each interval andcompared for efficacy to the data from all other formulations. Table 8summarizes the mean mortality data of all formulations at the statedobservation intervals.

Solutions A, B and F demonstrated a similar level of activity, and alldemonstrated markedly improved dry residue pesticidal activity relativeto both neem oil alone (Solution C), acetophenone alone (Solution D),and essential oils alone (Solution E), particularly at earlier timepoints between 12 hours and 120 hours.

TABLE 8 Mean % Mortality of 8-Day Old Residues. 0 HR 4 HR 8 HR 12 HR 24HR 48 HR 72 HR 96 HR 120 HR 144 HR Control 0.0% 0.0% 0.0% 0.0% 0.0% 0.0%0.0% 0.0% 0.0% 0.0% Solution A 0.0% 0.0% 10.0% 40.0% 65.0% 75.0% 90.0%95.0% 95.0% 100.0% Solution B 0.0% 0.0% 10.0% 25.0% 55.0% 80.0% 90.0%90.0% 90.0% 90.0% Solution C 0.0% 0.0% 0.0% 0.0% 0.0% 5.0% 5.0% 5.0%5.0% 5.0% Solution D 0.0% 0.0% 5.0% 5.0% 10.0% 25.0% 45.0% 45.0% 65.0%80.0% Solution E 0.0% 0.0% 0.0% 0.0% 0.0% 10.0% 10.0% 25.0% 30.0% 30.0%Solution F 0.0% 10.0% 20.0% 35.0% 65.0% 75.0% 90.0% 100.0% 100.0% 100.0%

Example 7—Prolonged Residual Pesticidal Activity

This example illustrates the prolonged residual pesticidal activity ofcombinations of neem oil, acetophenone, and a surfactant against bedbugs. The method used in this example facilitates assessment of thenecessary retreatment interval for a pesticidal composition. A solutioncomprising 5.5% neem oil by weight, 15.5% acetophenone by weight, 8%natural oils (lemongrass oil, spearmint oil, clove oil, and wintergreenoil) by weight and 5.0% ethoxylated castor oil by weight was preparedand combined with an appropriate amount of isopropyl alcohol as acarrier diluent. 1.0 mL of each solution was applied to unpaintedplywood surfaces, 90 millimetres in diameter, contained in petri dishes.Five replicates were done as a Treated Group, and five replicates weredone for an untreated negative Control Group tested concurrently. AllTreated Group substrates were treated at the beginning of theexperiment, then allowed to air dry until the time of infestation. OnDay 1, adult bed bugs were infested either immediately after treatment,or two hours after treatment (when the substrate was dry). On followingdays until Day 30, adult bed bugs were infested onto replicates ofsubstrates treated on Day 1 and air-dried since. At intervals afterinfestation of bed bugs each day, the number of bed bugs killed in theintervening period was counted. Adult bed bugs were counted dead ifunresponsive when stimulated.

The percentage of dead adult bed bugs was calculated for each dailyinterval and compared for efficacy to the data from the Control Group.Table 9 presents the mean mortality data for the Treated and ControlGroups for up to 27 days after the Day 1 treatment, at the 15-dayobservation interval. While the Controls in this experiment exhibitedhigher than normal mortality (perhaps because of contamination oftreated substrates or due to glue epoxy used to seal the substrateswithin petri dishes) the Treated Groups nonetheless exhibitedsignificantly improved pesticidal activity when compared with theControl Groups for treatments up to 27 days old.

TABLE 9 Mean % Mortality of Compositions after Prolonged Dry Times,Observed 15 Days after Infestation Days After Treatment, Prior toInfestation 1 2 3 4 5 6 7 8 9 10 11 12 13 14 % Treated 100 100 100 100100 100 100 100 100 100 100 83 97 87 Mortality Group Control 40 57 40 1323 43 0 23 7 10 30 37 10 0 Group Days After Treatment, Prior toInfestation 15 16 17 18 19 20 21 22 23 24 25 26 27 % Treated 100 97 100100 90 87 90 77 N/A* 70 90 53 60 Mortality Group Control 19 36 17 32 3343 50 13 10 24 12 6 37 Group *N/A = data not available

Example 8—Prevention of Bed Bug Egg Emergence

This example illustrates the prevention of egg emergence by acomposition including neem oil, acetophenone, and an appropriatesurfactant. The dry residue prevention of bed bug egg emergence iscompared among different methods of applying the composition and to anuntreated control group. A solution comprising 5.5% neem oil by weight,15.5% acetophenone by weight, 8% natural oils (lemongrass oil, spearmintoil, clove oil, and wintergreen oil) by weight and 5.0% ethoxylatedcastor oil by weight was prepared and combined with an appropriateamount of isopropyl alcohol as a carrier diluent. Three differentTreated Groups were prepared, one of filter paper treated with 1.0 mL ofsolution and allowed to air dry prior to introduction of eggs, one offilter paper with eggs laid on it treated with 1.0 mL of solution addedto the edge of the substrate and allowed to wick underneath the eggs,and one where eggs were sprayed directly. Five replicates for eachTreated Group, and five negative Control Group were tested concurrently.

At daily intervals, the numbers of hatched and unhatched eggs present inthe sealed dishes were counted and compared to other Treated Groups andthe Control Group. One egg was counted as “hatched” for every new nymphpresent in the petri dish when compared with the prior interval.

While the eggs in the Control Group hatched at the predicted interval ofapproximately 7 days, none of the eggs in any of the Treated Groups hadhatched by experiment's end 16 days post-treatment. No difference wasobserved between spray treatments, wet treatments, and dry residuetreatments. FIG. 1 shows the egg emergence data of the treated groups atthe stated daily intervals (the three treated groups having identicaldata sets) as compared to the Untreated Control.

Table 10 summarizes the prolonged dry residual egg emergence data from asimilar study of the same formulation as described above, over a longerperiod of time. 1.0 mL of the composition was dried for two hours priorto introduction of bed bug eggs, and completely prevented egg eclosionup to 19 days after its application to a filter paper substrate.

TABLE 10 Mean % Bed Bug Egg Eclosion Observed 15 days after Infestation.Days After Treatment 1 2 3 4 5 6 7 8 9 10 11 12 13 % Treated 0 0 0 0 0 00 0 0 2 0 0 0 Eclosion Group Control 59 56 39 49 51 33 55 53 66 81 72 7067 Group Days After Treatment 14 15 16 17 18 19 20 21 22 23 24 25 %Treated 0 0 0 0 0 0 7 27 33 N/A* 100 100 Eclosion Group Control 100 10099 100 100 100 100 100 97 100 100 100 Group *N/A = data not available

Example 9—Prevention of Cockroach Egg Emergence

The dry residue prevention of cockroach egg emergence was compared byexposing cockroach eggs (grouped as oothecae) to the composition and toan untreated control substrate. A solution comprising 22% neem oil byweight, 73% acetophenone by weight and 5.0% ethoxylated castor oil byweight was prepared and applied to filter paper at a rate of 800 ft²/galof solution. Following air-drying, treated paper was sealed insideplastic tubes (10 cm×3 cm diam.) along with gravid female cockroachescontaining eggs. Female cockroaches and eggs were exposed to suchtreated or control (untreated) papers for 15 days after initialtreatment. Ten replicates for each Treated Group, and ten negativeControl Group were tested concurrently.

At daily intervals, the numbers of hatched and unhatched eggs present inthe sealed tubes were counted and compared to the Control Group. One eggfrom each ootheca was counted as “hatched” for every new nymph presentin the tube when compared with the prior interval.

While the eggs in the Control Group hatched at the predicted interval of1-14 days, none of the eggs in the Treated Group had hatched byexperiment's end, 14 days post-treatment. FIG. 2 shows the egg emergencedata of the treated group at the stated daily intervals as compared tothe Untreated Control.

Both cockroaches and bed bugs are arthropods. Cockroaches belong to amore primitive taxonomic order, Blattellidae (although some commentatorsconsider cockroaches to belong to the order Orthoptera), than bed bugs,which belong to the order Hemiptera. Both cockroaches and bed bugsreproduce relatively quickly compared to other arthropods. Without beingbound by theory, this rapid reproduction may contribute to the abilityof these pests to survive insecticide treatments. Preventing eggemergence of bed bugs, cockroaches and other arthropods can thereforepotentially assist in eliminating these pests.

Example 10—Prevention of Oviposition and Egg Emergence in Bed Bugs

This example illustrates the prevention of egg emergence of acombination of neem oil and acetophenone, as compared with neem oilalone.

A concentrated solution, ‘Solution B,’ including 25% neem oil by weight,70% acetophenone by weight, and 5.0% ethoxylated castor oil by weightwas prepared. Dilutions of this concentrated solution were prepared,each containing ethanol as the carrier diluent. Dilutions containing 15%of Solution B (final concentration of 3.75% neem oil and 10.5%acetophenone by weight)—or greater—killed 100% of adults infested on thetreated surface and no eggs were laid. Dilutions of 10% or less ofSolution B were insufficient to kill adult bed bugs before eggs werelaid on the treated substrates in these groups; these dilutions weremonitored for oviposition and eclosion, and are compared to positivecontrol treatments of neem oil alone (10% solution in diluent) andnegative controls treated only with the carrier diluent. ‘Formulation A’included 10% neem oil by weight diluted in ethanol, ‘Formulation B’contained 10% by volume of the concentrated Solution B described abovediluted in ethanol (final concentration of 2.5% neem oil and 7%acetophenone by weight); ‘Formulation C’ included 1% by volume of theconcentrated Solution B (final concentration of 0.25% neem oil and 0.7%acetophenone by weight); and ‘Formulation D’ included 0.1% by volume ofthe concentrated Solution B (final concentration of 0.025% neem oil and0.07% acetophenone by weight).

Table 11 summarizes egg emergence and oviposition observations for thetested compositions and controls. Oviposition was seen on 10-day-old drytreatments of all the above solutions and controls, but wassignificantly reduced on the sample treated with a 10% dilution ofSolution B (Formulation B). Eclosion was observed on both negativecontrols and Formulation A (neem oil only) treatments, and on dilutionsof the concentrated Solution B of 0.1% (Formulation D) and lowerconcentrations. No egg emergence was exhibited on dilutions of 1.0% ofthe concentrated Solution B or more (Formulation B and C).

TABLE 11 Eclosion and Oviposition Observations of a Serial Dilution ofan Exemplary Composition, Compared with Control and Neem Oil Alone,Observed 10-13 Days after Infestation. 10 Day 11 Day 12 Day 13 Day #eggs # emerged # eggs # emerged # eggs # emerged # eggs # emergedNegative Control 29 0 31 0 31 11 31 11 Formulation A 22 0 23 0 25 8 25 8(10% Neem Oil) Formulation B 4 0 4 0 4 0 4 0 (2.5% Neem Oil + 7%Acetophenone) Formulation C 18 0 19 0 18 0 18 0 (0.25% Neem Oil + 0.7%Acetophenone) Formulation D 35 0 36 0 34 9 34 9 (0.025% Neem Oil + 0.07%Acetophenone)

Example 11—Prevention of Egg Emergence by Various Pesticidal NaturalOils

This example illustrates the prevention of egg emergence of formulationsincluding a natural oil and acetophenone. Solutions were preparedaccording to Table 12 below, comprising 2.5% by weight active oilingredient, 5.0% by weight solvent (either ethyl lactate oracetophenone), and an appropriate amount of water as a carrier diluent.Treated Groups for each solution were prepared by treating filter paper,90 mm in diameter, with 1.0 mL of solution and allowed to air dry fortwo hours. Five bed bug eggs were added to each treated dish, two hoursafter treatment. Immediately after infestation, and at 1-, 2-, and3-week intervals thereafter, the numbers of hatched and unhatched eggspresent in the sealed dishes were counted and compared to other TreatedGroups. One egg was counted as “hatched” for every new nymph present inthe petri dish when compared with the prior interval. Table 12 comparesthe mean % egg eclosion of the treated groups at three weekspost-infestation. The maximum mortality data obtained in Example 2,above, are included for each formulation, for comparison purposes.

All dishes treated with 2.5% by weight natural oils and 5.0% by weightethyl lactate exhibited some eclosion at all weekly observationintervals (up to 80% eclosion for combinations of ethyl lactate withclove oil, thyme oil, garlic oil, lavender oil, and lime oil).Combinations of 2.5% by weight cinnamon oil, thyme oil, garlic oil,anise oil, geraniol, and geranium oil with 5.0% acetophenone by weightresulted in complete prevention of egg eclosion across all observationintervals. Combinations of 2.5% by weight clove oil, eugenol, andoregano oil exhibited some increased prevention of egg emergencerelative to solutions of ethyl lactate, although some egg emergence wasobserved. Solutions with 2.5% clove oil, eugenol, and oregano oil allexhibited complete prevention of egg eclosion when combined with 15.5%acetophenone by weight. Among those tested, the natural oils thatexhibited stronger insecticidal activity on adult bed bugs alsogenerally exhibited stronger ovicidal activity and prevention of eggemergence.

TABLE 12 Mean % Eclosion of Formulations Incorporating Various NaturalOils. Pesticidal Max % Eclosion (3 Natural Oil Solvent mortality weekspost-infest.) Cinnamon Oil Acetophenone 100%  0% Cinnamon Oil EthylLactate 100% 40% Clove Oil Acetophenone 100% 20% Clove Oil Ethyl Lactate100% 80% Eugenol Acetophenone 100% 20% Eugenol Ethyl Lactate 100% 40%Oregano Oil Acetophenone 100% 20% Oregano Oil Ethyl Lactate 100% 40%Thyme Oil Acetophenone 100%  0% Thyme Oil Ethyl Lactate 100% 80% GarlicOil Acetophenone  90%  0% Garlic Oil Ethyl Lactate 100% 80% Anise OilAcetophenone 100%  0% Anise Oil Ethyl Lactate  30% 40% Geranium OilAcetophenone 100%  0% Geranium Oil Ethyl Lactate  90% 60% Lime OilAcetophenone  89%  0% Lime Oil Ethyl Lactate  45% 80% Peppermint OilAcetophenone 100%  0% Peppermint Oil Ethyl Lactate  55% 60% Lavender OilAcetophenone 100%  0% Lavender Oil Ethyl Lactate  40% 80% Neem OilAcetophenone 100% N/A** Neem Oil Ethyl Lactate  40% N/A** Control None 30% 100%  **N/A: Test not performed

Example 12: Prevention of Egg Emergence with Various Solvents

This example illustrates the dry residual pesticidal activity offormulations including neem oil and various organic solvents includingalcohols, ketones, esters and carboxylic acids. Solutions were preparedusing 5.5% by weight neem oil; the percent by weight of organic solventindicated in Table 13 and an appropriate amount of isopropanol as acarrier diluent. Treated Groups for each solution were prepared bytreating filter paper, 90 mm in diameter, with 1.0 mL of solution andallowing it to air dry for four hours. Five eggs were added to eachtreated dish, four hours after treatment. Immediately after infestation,and at 1-, 2-, and 3-week intervals thereafter, the numbers of hatchedand unhatched eggs present in the sealed dishes were counted andcompared to other Treated Groups. One egg was counted as “hatched” forevery new nymph present in the petri dish when compared with the priorinterval. Table 13 compares the % egg eclosion of the treated groups atthe 3-week observation interval. The maximum mortality data obtained inExample 3, above, are included for comparison purposes.

A number of the tested organic solvents, from the classes of alcohols,ketones, esters and carboxylic acids, proved effective at preventing eggeclosion in combination with neem oil. Solvents that included at leastone aryl group were generally more effective at preventing egg emergencethan solvents that contained only alkyl groups. Alkyl aryl ketones wereconsistently effective solvents, and small aryl alcohols, aryl alkylalcohols, aryl aryl ketones, and alkyl aryl esters also proved effectiveat preventing emergence in combination with neem oil. Among thosetested, the organic solvents that exhibited stronger insecticidalactivity on adult bed bugs generally also exhibited stronger ovicidalactivity and prevention of egg emergence.

TABLE 13 % Bed Bug Egg Eclosion Observed 3 Weeks after Infestation.Class of % Solvent Max. % Solvent Formula (w/w) Compound name MortalityEclosion Alcohol X = CH(OH) Alkyl Alk-X—H alcohols Alk = butyl 11.261-Butanol  40% 100%  Alk = hexyl 15.52 1-Hexanol  40% 0% Alk =ethyl-pentyl 19.78 2-Ethyl-1-hexanol 100% 0% (Branched alkyl) Alk =decyl 24.04 1-Decanol 100% 0% Isoalcohols Alk₁-X-Alk₂ Alk₁ = ethyl 11.262-Butanol  20% 100%  Alk₂ = methyl Cyclohexanol 15.21 Cyclohexanol  60%60%  Aryl alcohol Ar—X—H Ar = phenyl 16.42 Benzyl alcohol 100% 0%Aryl-alkyl Ar—X-Alk alcohol Ar = phenyl 18.56 1-Phenylethanol 100% 0%Alk = methyl Aldehyde and Ketone X = (C═O) Aldehyde Ar—X—H Ar = phenyl16.12 Benzaldehyde 100% 0% Alkyl-Alkyl Alk₁-X-Alk₂ ketone Alk₁ = methyl19.17 Methylcyclohexylketone  70% 80%  Alk₂ = cyclohexyl Cyclohexanone14.91 Cyclohexanone  50% 40%  Aryl-Alkyl Ar—X-Alk ketone Ar = phenyl18.25 Acetophenone 100% 0% Alk = methyl Ar = 4-methylphenyl 20.384′-Methylacetophenone 100% 0% Alk = methyl Ar = 2,4- 22.512′,4′-Dimethylacetophenone 100% 0% dimethylphenyl Alk = methyl Ar = 3,4-22.51 3′,4′-Dimethylacetophenone 100% 0% dimethylphenyl Alk = methyl Ar= phenyl 20.69 Propiophenone 100% 0% Alk = ethyl Ar = 4-methylphenyl22.51 4′-Methylpropiophenone 100% 0% Alk = ethyl Ar = phenyl 22.51Butyrophenone 100% 0% Alk = propyl Ar = phenyl 22.51 Isobutyrophenone100% 0% Alk = isopropyl Ar = phenyl 24.64 Valerophenone 100% 0% Alk =butyl Ar = phenyl 26.77 Hexanophenone 100% 0% Alk = pentyl Aryl-arylAr₁—X—Ar₂ ketone Ar₁ = 2,4- 37.4 2,2′-4,4′ 100% 0% dihydroxyphenylTetrahydroxybenzophenone Ar₂ = 2,4- dihydroxyphenyl Carboxylic Acids andEsters X = (C═O)—O Alkyl-alkyl Alk₁-X-Alk₂ ester Alk₁ = methyl 13.38Ethyl acetate  30% 100%  Alk₂ = ethyl Alk₁ = methyl 30.122-tert-Butylcyclohexylacetate 100% 20%  Alk₂ = 2-tert- butylcyclohexylAryl acid Ar—X—H Ar = phenyl 18.55 Benzoic acid 100% 0% Aryl-alkylAr—X-Alk ester Ar = 4-hydroxyphenyl 27.27 Propyl-4-hydroxybenzoate 100%0% Alk = propyl

Example 13—Insecticidal Knockdown Activity

This example illustrates the insecticidal knockdown activity ofcombinations of neem oil or derivatives thereof with acetophenoneagainst bed bugs, when compared with knockdown activity of neem oil orderivative alone and acetophenone alone. Six solutions were prepared:‘Solution A’ included 5.5% neem oil by weight, 1.25% ethoxylated castoroil by weight and 18.25% acetophenone by weight, and isopropanol as acarrier solvent; ‘Solution B’ included 5.5% neem oil by weight, 1.25%ethoxylated castor oil by weight, 18.25% acetophenone by weight, andwater as a carrier solvent; ‘Solution C’ included 5.5% neem oil byweight, 1.25% ethoxylated castor oil by weight, and water as a carriersolvent; ‘Solution D’ included 18.25% acetophenone by weight, 1.25%ethoxylated castor oil by weight, and water as a carrier solvent;‘Solution F’ included 0.3% azadirachtin A by weight, 1.25% ethoxylatedcastor oil by weight %, 18.25% acetophenone by weight, and water as acarrier solvent; and ‘Solution F’ included 0.3% azadirachtin A byweight, 1.25% ethoxylated castor oil by weight, and water as a carriersolvent. Adult bed bugs were infested on to petri dishes containingfilter paper, 90 millimetres in diameter. Bed bugs were treated byapplying 5 microliters of each solution to the ventral side. Mortalitywas assessed at intervals of 30 minutes, and 1-, 2-, 4-, 6-, 8-, 10-,24-, 100-, and 342-hours after treatment. Bed bugs were counted dead ifunresponsive when stimulated. The percentage of dead adult bed bugs wascalculated and compared to data from all other formulations. Table 14summarizes mortality data of respective formulations at the statedintervals.

The neem/acetophenone (Solutions A and B) and azadirachtin/acetophenone(Solution C) combinations performed better as knockdown killers thanneem alone (Solution D), acetophenone alone (Solution E), andazadirachtin alone (Solution F).

TABLE 14 % Mortality of Neem Oil and Azadirachtin as Knockdown Killersof Adult Bed Bugs. Time (hours) 0 0.5 1 2 4 6 8 10 24 100 342 %Mortality Solution A (5.5% neem oil, 0 80 80 80 80 90 90 100 100 100 10018.25% acetophenone, 75% isopropanol) Solution B (5.5% neem oil, 18.25%0 60 60 60 60 70 80 80 90 80 100 acetophenone, 75% water) Solution C(0.3% azadirachtin A, 0 30 30 30 30 40 70 80 100 100 100 18.25%acetophenone, 80.2% water) Solution D (5.5% neem oil, 0 30 40 40 50 5050 50 50 60 50 93.25% water) Solution E (18.25% 0 40 40 40 40 40 40 4030 30 100 acetophenone, 80.5% water) Solution F (0.3% azadirachtin A, 00 0 0 0 0 0 0 0 0 10 98.45% water) Water 0 0 0 0 0 0 0 0 0 0 0 UntreatedControl 0 0 0 0 0 0 0 0 0 0 0

Example 14—Broad Spectrum Pesticide Activity

This example illustrates the dry residue pesticidal activity of acombination of natural oil and solvent against arthropods (includinginsects) other than bed bugs. The tested arthropods were Germancockroach (Blattella germanica). Smoky Brown cockroach (Periplanetafuliginosa), American cockroach (Periplaneta americana), cellar spider(Pholcus phalangiodes) cat flea (Ctenocephalides felis), tick (Ixodideafamily), fire ant (Solenopsis Invicta), termite (Reticulitermesflavipes), black carpenter ant (Camponotus pennsylvanicus), pavement ant(Tetramorium caespitum), field ant (Formica sp.), moisture ant (Lasiussp.), wood ant (Formica rufa), house fly (Musca domestica), bottle fly(Lucilia sericata), giant silverfish (Ctenolepisma longicaudata),firebrat (Thermobia domestica), bean aphid (Aphis fabae), and pea aphid(Acyrthosiphon pisum). A solution of 5.5% neem oil by weight, 15.5%acetophenone by weight, 2.65% natural oils (lemongrass oil, vanillin,and wintergreen oil) by weight and 1.25% ethoxylated castor oil byweight was combined with an appropriate amount of isopropyl alcohol as acarrier diluent. 1.0 mL of the solution was applied to filter papersurfaces, 90 millimetres in diameter, contained in petri dishes (theTreated Groups). Untreated Control replicates were tested concurrently.Treated substrates were allowed to air dry for two hours prior toinfestation with a known number of adult arthropods. Dishes wereinfested according to the following schedule: three replicates of threeadults apiece were prepared for American and Smoky Brown cockroaches;three replicates of five adults apiece were prepared for Germancockroaches; nine replicates of one adult apiece were prepared forcellar spiders; and three replicates of 10 adults apiece were preparedfor ticks, ants, termites, flies, aphids, silverfish, firebrats, and catfleas. At 1-, 4-, and 24-hour intervals following the addition ofarthropods, the number of arthropods killed in the intervening periodwas observed. The adult arthropods were counted dead if they wereunresponsive when stimulated.

The percentage of dead adult arthropods was calculated for 1-, 4-, and24-hour intervals following infestation and compared for efficacy to thedata of the Control Groups. Table 15 summarizes the mean mortality dataof the treatment against each arthropod at the stated intervals. Thetested composition killed 100% of all arthropods by the 24-hourobservation interval, and exhibited strong pesticidal activity againstsome species at the 4-hour observation interval.

TABLE 15 Mean % Mortality of 2-Hour Dried Compositions AgainstArthropods. Treated/ Mean % Mortality Insect Control 0 hrs 1 hrs 4 hrs24 hrs Smoky Brown cockroach Treated 0 0 45 100 Smoky Brown cockroachControl 0 0 0 0 German cockroach Treated 0 0 93 100 German cockroachControl 0 0 0 0 American cockroach Treated 0 0 66 100 American cockroachControl 0 0 0 0 Cellar Spider Treated 0 11 33 100 Cellar Spider Control0 0 0 33 Cat Flea Treated 0 100 100 100 Cat Flea Control 0 0 0 0 TickTreated 0 7 100 100 Tick Control 0 0 0 0 Fire Ant Treated 0 100 100 100Fire Ant Control 0 0 10 100 Termite Treated 0 100 100 100 TermiteControl 0 0 20 20 Carpenter Ant Treated 0 10 80 100 Carpenter AntControl 0 0 0 0 Pavement Ant Treated 0 100 100 100 Pavement Ant Control0 0 0 0 Field Ant Treated 0 100 100 100 Field Ant Control 0 0 0 0Moisture Ant Treated 0 100 100 100 Moisture Ant Control 0 0 0 70 WoodAnt Treated 0 100 100 100 Wood Ant Control 0 0 0 0 House Fly Treated 055 100 100 House Fly Control 0 0 0 80 Bottle Fly Treated 0 95 100 100Bottle Fly Control 0 0 0 0 Giant Silverfish Treated 0 0 22 100 GiantSilverfish Control 0 0 0 0 Firebrat Treated 0 0 40 100 Firebrat Control0 0 0 0 Bean aphid Treated 0 10 25 100 Bean aphid Control 0 0 0 22 PeaAphid Treated 0 0 95 100 Pea Aphid Control 0 0 0 33

Example 15—Broad Spectrum Pesticide Activity

This example illustrates the dry residue pesticidal activity of acombination of natural oil and solvent against arthropods (includinginsects, arachnids, millipedes and centipedes) other than bed bugs. Thetested arthropods were granary weevil (Sitophilus granarius), maizeweevil (Sitophilus zeamais), confused flour beetle (Tribolium confusum),rusty grain beetle (Cryptolestes ferrugineus), dust mite(Dermatophagoides farinae), millipede (Cylindroiulus caeruleocinctus),centipede (Strigamia aluminata), sowbug (Oniscus asellus), orabatid mite(Haplozeter sp.), house cricket (Acheta domestica), black widow spider(Latrodectus mactans), brown recluse spider (Loxosceles reclusa),pharaoh ant (Monomorium pharaonis).

A solution of 5.5% neem oil by weight, 18.25% acetophenone by weight and1.25% ethoxylated castor oil by weight was combined with an appropriateamount of isopropyl alcohol as a carrier diluent (“treatment A”), oralternatively, a solution comprising 22% neem oil by weight, 73%acetophenone by weight and 5.0% ethoxylated castor oil by weight(“treatment B”) was prepared. 0.64-1.2 mL of the solution was applied tofilter paper surfaces, 90 millimetres in diameter, contained in petridishes (the Treated Groups). Untreated Control replicates were testedconcurrently.

Treated substrates were allowed to air dry for 2 hours (treatment A) or4 hours (treatment B) prior to infestation with a known number of adultarthropods. Dishes were infested according to the following schedule:five replicates of five adults apiece were prepared for granary weevils,maize weevils, confused flour beetles and rusty grain beetles; threereplicates of 10 adults apiece were prepared for millipedes; fourreplicates of 5 adults apiece were prepared for centipedes and pharaohants; 6 replicates of 5 adults apiece were prepared for sowbugs and dustmites; one replicate of 30 adults was prepared for orabatid mites; tworeplicates of 5 adults apiece were prepared for house crickets; and 20replicates of 1 adult apiece were prepared for black widow spiders andbrown recluse spiders. At 1-, 4-, and 24-hour intervals following theaddition of arthropods, the number of arthropods killed in theintervening period was observed. The adult arthropods were counted deadif they were unresponsive when stimulated.

The percentage of dead adult arthropods was calculated for 1-, 4-, and24-hour intervals following infestation and compared for efficacy to thedata of the Control Groups. Table 16 summarizes the mean mortality dataof the treatment against each arthropod at the stated intervals. Thetested composition killed 100% of all arthropods by the 24-hourobservation interval, and exhibited strong pesticidal activity againstsome species at the 1- and 4-hour observation interval.

TABLE 16 Mean % Mortality of 2- or 4-Hour Dried Compositions AgainstArthropods Treated/ Mean % Mortality Insect Control 0 hrs 1 hrs 4 hrs 24hrs Granary Weevil Treated 0 100 100 100 Granary Weevil Control 0 0 0 0Maize Weevil Treated 0 100 100 100 Maize Weevil Control 0 0 0 0 ConfusedFlour Beetle Treated 0 0 0 100 Confused Flour Beetle Control 0 0 0 0Rusty Grain Beetle Treated 0 100 100 100 Rusty Grain Beetle Control 0 00 0 Dust Mite Treated 0 100 100 100 Dual Mite Control 0 0 3 7 Millipede*Treated 0 0 83 100 Millipede* Control 0 0 3 13 Centipede* Treated 0 10100 100 Centipede* Control 0 0 0 5 Sowbug* Treated 0 0 100 100 Sowbug*Control 0 0 0 0 Orabatid Mite* Treated 0 73 100 100 Orabatid Mite*Control 0 0 0 0 House Cricket* Treated 0 80 100 100 House Cricket*Control 0 0 0 0 Black Widow Spider* Treated 0 0 0 100 Black WidowSpider* Control 0 0 0 0 Brown Recluse Spider* Treated 0 0 0 80 BrownRecluse Spider* Control 0 0 0 0 Pharaoh Ant* Treated 0 0 95 100 PharaohAnt* Control 0 0 0 0 (no asterisk = exposed to 2 h dry residualtreatment A) (*= exposed to 4 h dry residual treatment B)

Example 16—Dry Residual Pesticide Activity Against Insecticide-ResistantInsects

This example illustrates the dry residue pesticidal activity ofexemplary compositions against bed bugs resistant to pyrethroidinsecticides, a recognized problem in eliminating bed bug infestations(see Romero). A formulation of 5.5% neem oil by weight, 15.5%acetophenone by weight, 8% natural oils (lemongrass oil, spearmint oil,clove oil, and wintergreen oil) by weight and 5.0% ethoxylated castoroil by weight was prepared and combined with an appropriate amount ofisopropyl alcohol as a carrier diluent (the Treated Group). Aconcentrate formulation of the common pyrethroid insecticide Suspend® SCcontaining 4.75% deltamethrin by weight diluted according to the highest(strongest) rate allowed by the label was employed as a Positive ControlGroup. 1.0 mL of each solution was applied to filter paper surfaces, 90millimetres in diameter, contained in petri dishes, and allowed to dryfor two hours. Five replicates of each Treated Group, Positive ControlGroup, and a Negative Control Group were tested concurrently. Adult bedbugs from a field-collected strain were added to each treated surface.Mortality of bed bugs was observed at specified intervals afterinfestation on substrates. The adult bed bugs were counted dead if theywere unresponsive when stimulated.

The percentage of dead adult bed bugs at 0-, 1-, 4-, 8-, 12-, 24-, and72-hour intervals on Treated Group were compared against those infestedon the Positive Control (deltamethrin-treated) and Negative ControlGroups. FIG. 3 summarizes the results as tested on filter paper. Bedbugs infested on deltamethrin (Positive Control Group) exhibited meanmortality of 10% by the 72-hour interval, which was statisticallyinsignificant in comparison with Negative Controls. The testedformulation including neem oil and acetophenone produced 100% mortalityby the 24-hour interval.

Example 17—Repellency of Exemplary Compositions

This example illustrates the repellency characteristics of an exemplarycomposition according to one embodiment. Where it is desired to have aninsecticide act by killing or otherwise disrupting the life cycle ofadult insects, nymphs, and their eggs, rather than merely dispersingthem, repellent characteristics of the composition utilized may bereduced or minimized in some embodiments.

In this example, bed bug mortality was evaluated on a treated surfacewith an untreated crevice harbourage available, and the percentage ofbed bugs that retreated to the untreated crevice was measured toevaluate the repellency of the tested compositions. Four solutions wereprepared, each containing isopropanol as a carrier diluent: ‘Solution A’included 5.5% neem oil by weight, 15.5% acetophenone by weight, 8%natural oils (lemongrass oil, spearmint oil, and wintergreen oil) byweight and 5.0% surfactant by weight; ‘Solution B’ included 5.5% neemoil by weight, 15.5% acetophenone by weight, and 5.0% surfactant byweight; ‘Solution C’ included 5.5% neem oil by weight, and 5.0%surfactant by weight; and ‘Solution D’ included 5.5% neem oil alone byweight. The surfactant used in all solutions was ethoxylated castor oil.Ninety-millimetre diameter filter paper substrates were prepared inpetri dishes, on which were affixed small wooden blocks notched on oneside, the notch forming a small crevice out of contact with the filterpaper where insects could shelter. For the Treated Groups 1.0 mL of eachsolution was applied to the exterior of the block, leaving the creviceuntreated, and 1.0 mL of each solution was applied directly to thefilter paper substrate. A fifth untreated group was tested concurrentlyas a negative Control Group. Treated substrates were allowed to dry fortwo hours before infestation with adult bed bugs.

Immediately after treatment and at 1-, 4-, and 8-hour intervals afterinfestation of bed bugs to each group, the bed bugs were observed formortality and whether they preferred to stay on the treated filterpaper, or locate within the untreated crevice. Table 17 summarizes theobservations of each Group immediately after infestation and at 1-, 4-,and 8-hour intervals post-infestation. Compositions A and B, whichincluded neem oil in combination with acetophenone, exhibited a lesserdegree of repellency (i.e. fewer bed bugs were counted in the untreatedcrevice) than compositions including neem oil alone, with or withoutsurfactant (compositions C and D).

TABLE 17 Mean Repellency Data. 0-hour 1-hour 4-hour 8-hour % % % % % % %Live Live Live % Live Live Live Live Live In Out In Out % In Out % InOut % Solution Crev. Crev. Crev. Crev. Dead Crev. Crev. Dead Crev. Crev.Dead A 0 100 0 100 0 0 22 78 0 0 100 B 0 100 10 90 0 0 0 100 0 0 100 C 0100 40 60 0 70 30 0 20 10 70 D 0 100 100 0 0 80 20 0 60 0 40 Control 0100 50 50 0 50 50 0 60 40 0

Example 18—Testing of Various Substrates

This example illustrates the pesticidal activity of a compositionaccording to an exemplary embodiment on a variety of surfaces. Inparticular, the example demonstrates the dry residue pesticidal activityof an exemplary formulation on several substrates where bed bugs areknown to live, nest, and reproduce indoors. A solution including 5.5%neem oil by weight, 15.5% acetophenone by weight, 8% natural oils(lemongrass oil, spearmint oil, clove oil, and wintergreen oil) byweight and 5.0% ethoxylated castor oil by weight was prepared andcombined with an appropriate amount of isopropyl alcohol as a carrierdiluent. Four substrates were prepared: painted plywood, 100% cottonfabric, mattress swatch, and Berber carpet (glued to the petri dish toprevent the test bugs from climbing underneath the carpet to escape thetreated area). Five replicates were constructed for each Treated Groupand five replicates were constructed for untreated Control Groups ofeach substrate. 1.0 mL of the formulation was applied to each TreatedGroup and allowed to dry for two hours. Adult bed bugs were infested twohours after treatment. Bed bugs were observed for mortality immediatelyafter infestation and at 1-, 4-, 8-, 12-, 24-, and 72-hour intervalspost-infestation. Bed bugs were counted dead if unresponsive whenstimulated.

The percentage of dead adult bed bugs was calculated for each intervaland compared to the data for all other groups. Table 18 presents themean mortality data for the Treated and Control Groups over the statedintervals. Mortality of adult bed bugs for all Treated Groups was 100%at 24 hours and 100% for all treated surfaces excepting glued carpet(80% mortality) at 12 hours. This data indicates efficacy of the testedcomposition on a wide range of indoor surfaces.

TABLE 18 Mean % Bed Bug Mortality after Treatment on Various Substrates.Time (Hours) 0 1 4 8 12 24 72 Untreated 0 2 6 4 4 6 6 Plywood Treated 02 58 98 100 100 100 Plywood Untreated 0 0 2 2 6 8 16 Cotton Treated 0 2882 100 100 100 100 Cotton Untreated 0 2 2 4 4 4 12 Mattress Treated 0 4298 100 100 100 100 Mattress Untreated 0 0 0 0 0 0 0 Glued Carpet TreatedGlued 0 0 0 30 80 100 100 Carpet

Example 19—Residual Activity of Various Solvent/Oil Combinations

This example illustrates the dry residual pesticidal activity offormulations comprising varying pesticidal natural oils (oregano, cloveand cinnamon oils) with acetophenone as the polar aromatic solvent.Solutions were prepared using 5.5% by weight natural oil; the percent byweight of acetophenone indicated in Table 19 and an appropriate amountof isopropanol as a carrier diluent. The percent by weight of solventwas at a final concentration of 1.5 mol/kg. Solutions were also preparedof each natural oil alone (5.5% by weight with an appropriate amount ofisopropanol as a carrier diluent), and of acetophenone alone (thepercent by weight indicated in Table 19 with an appropriate amount ofisopropanol as a carrier diluent). Treated Groups for each solution wereprepared by treating filter paper, 90 mm in diameter, with 1.0 mL ofsolution and allowing it to air dry for four hours. A known number ofadults (usually 10) were added to each treated dish, four hours aftertreatment. Bed bug mortality was assessed immediately after infestationand at 1-hour, 2-hour, 4-hour, 6-hour, 8-hour, 10 hour, 12-hour, and24-hour intervals, and at 24-hour intervals thereafter until 14 daysafter infestation. Adult bed bugs were counted dead if they wereunresponsive when stimulated. Table 19 shows the maximum % mortality ofall treated groups and the time taken to reach maximum mortality.Combinations of a pesticidal oil and acetophenone were more effectivethan either the oil or acetophenone alone.

TABLE 19 Maximum % Mortality of Various Oils Alone or With AcetophenoneSolvent Max Oil Solvent % w/w Mortality Time LT50 Oil Controls Oreganooil — — 100% 72 h 18 h Clove oil — — 100% 53 h 17 h Cinnamon — —  90%218 h  22 h oil Oil + Acetophenone Oregano oil Acetophenone 18.25 100%24 h  6 h Clove oil Acetophenone 18.25 100% 24 h  8 h CinnamonAcetophenone 18.25 100% 53 h  8 h oil — Acetophenone 18.25 100% 53 h 17h

Example 20—Residual Activity of Various Oils in Combination withAcetophenone

This example illustrates the dry residual pesticidal activity offormulations comprising further pesticidal natural oils (thyme, garlicand neem oils) with acetophenone as the polar aromatic solvent.Solutions were prepared using 5.5% by weight natural oil; the percentageby weight of organic solvent indicated in Table 20 and an appropriateamount of isopropanol as a carrier diluent. Solvent was added to a finalconcentration of 1.5 mol/kg. Solutions were also prepared of eachnatural oil alone (5.5% by weight with an appropriate amount ofisopropanol as a carrier diluent), and of the polar organic solventalone (the percent by weight indicated in Table 20 with an appropriateamount of isopropanol as a carrier diluent). Treated Groups for eachsolution were prepared by treating filter paper, 90 mm in diameter, with1.0 mL of solution and allowing it to air dry for four hours. A knownnumber of adults (usually 10) were added to each treated dish, fourhours after treatment. Bed bug mortality was assessed immediately afterinfestation and at 1-hour, 2-hour, 4-hour, 6-hour, 8-hour, 10 hour,12-hour, and 24-hour intervals, and at 24-hour intervals thereafteruntil 14 days after infestation. Adult bed bugs were counted dead ifthey were unresponsive when stimulated. Table 20 shows the maximum %mortality of all treated groups and the time taken to reach maximummortality. Combinations of a pesticidal oil and acetophenone were moreeffective than either the oil or acetophenone alone.

TABLE 20 Maximum % Mortality of Various Oils Alone or With AcetophenoneSolvent Max Oil Solvent % w/w Mortality Time LT50 Oil Controls Oreganooil — 100%  24 h  8 h Clove oil — 100% 150 h 27 h Cinnamon — 100% 150 h37 h oil Thyme — 100% 150 h 36 h Garlic — 100% 150 h 22 h Neem oil — 10% — — Oil + Acetophenone Thyme Acetophenone 18.25 100%  10 h  6 hGarlic Acetophenone 18.25 100%  10 h  7 h Neem oil Acetophenone 18.25100%  8 h  4 h — Acetophenone 18.25 100%  48 h 11 h

Various references are mentioned or pertinent to the discussion herein,including for example the References listed below. The disclosures ofeach of the following references are incorporated by reference in theirentireties.

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The invention described herein is not to be limited in scope by thespecific aspects herein disclosed, since these aspects are intended asillustrations of several aspects of the invention. Any equivalentaspects are intended to be within the scope of this invention. Variousmodifications of embodiments of the invention in addition to those shownand described herein will become apparent to those skilled in the artfrom the foregoing description. Such modifications are also intended tofall within the scope of the appended claims and any claims hereafterintroduced. To the extent that they are not mutually exclusive,embodiments described above can be combined with one another to yieldfurther embodiments of the invention.

What is claimed is:
 1. A method of controlling pests comprising exposingthe pests or their eggs to a composition comprising a pesticidal naturaloil and/or a component thereof and/or a derivative thereof and a polararomatic solvent or an alkyl alcohol solvent.
 2. The method as definedin claim 1, wherein the pests comprise arthropods.
 3. The method asdefined in claim 2, wherein the arthropods comprise insects, arachnids,centipedes or millipedes.
 4. The method as defined in claim 3, whereinthe insects are of the orders Hemiptera, Hymenoptera, Blattodea,Isoptera, Diptera, Lepidoptera, Thysanoptera, Thysanura, Coleopteran,Siphonaptera, Phthiraptera, Psocidae, Dermaptera, or Orthoptera.
 5. Themethod as defined in claim 2, wherein the arthropods comprise bed bugs,cockroaches, flies, ants, ticks, fleas, sowbugs, pilbugs, centipedes,millipedes, spiders, silverfish, scorpions, aphids, scabies, lice, stinkbugs, moths, beetles, lace bugs, aphids, thrips, moths, leafminers,grasshoppers, crickets, locusts, leafhoppers, planthoppers, psyllids,scale insects, midges, worms, milkweed bugs, mealy bugs, weevils, ricebugs, coffee bugs, vegetable bugs, corn borers, or mites.
 6. The methodas defined in claim 2, wherein the arthropods comprise bed bugs (Cimexlectularius), German cockroaches (Blattella germanica), Smoky Browncockroaches (Periplaneta fuliginosa), American cockroaches (Periplanetaamericana), cat fleas (Ctenocephalides felis), fire ants (SolenopsisInvicta), black carpenter ants (Camponotus pennsylvanicus), pavementants (Tetramorium caespitum), field ants (Formica sp.), moisture ants(Lasius sp.), wood ants (Formica rufa), house flies (Musca domestica),bottle flies (Lucilia sericata), giant silverfish (Ctenolepismalongicaudata), firebrats (Thermobia domestica), bean aphids (Aphisfabae), pea aphids (Acyrthosiphon pisum), termites (Reticulitermesflavipes), granary weevils (Sitophilus granarius), maize weevils(Sitophilus zeamais), confused flour beetles (Tribolium confusum), rustygrain beetles (Cryptolestes ferrugineus), dust mites (Dermatophagoidesfarinae), millipedes (Cylindroiulus caeruleocinctus), centipedes(Strigamia aluminata), sowbugs (Oniscus asellus), orabatid mites(Haplozetes sp.), house crickets (Acheta domestica), black widow spiders(Latrodectus mactans), brown recluse spiders (Loxosceles reclusa), orpharaoh ants (Monomorium pharaonis).
 7. The method as defined in claim1, wherein the pesticidal natural oil and/or component thereof and/orderivative thereof comprises neem oil, clove oil, peppermint oil,cinnamon oil, thyme oil, oregano oil, garlic oil, anise oil, geraniumoil, lime oil, lavender oil, eugenol, or a combination thereof.
 8. Themethod as defined in claim 1, wherein the polar aromatic solvent isselected from the group consisting of: aryl alcohols, aryl-alkylalcohols, aryl aldehydes, aryl-ketones, aryl-alkyl ketones, aryl-arylketones, aryl carboxylic acids, aryl esters, aryl-alkyl esters,aryl-aryl esters, aryl-alkyl ethers, and aryl-aryl ethers.
 9. The methodas defined in claim 1, wherein the polar aromatic solvent comprises acompound having the structure:

wherein R₁ can be:

and wherein R₂, R₃, R₄, R₅ and R₆ can independently be —H, or an alkylgroup, alkenyl group or alkynl group, including e.g. a methyl, ethyl,propyl, isopropyl, butyl, or pentyl group or the like, or an —OH groupor a halo functional group, or an alkyl, alkenyl or alkynyl groupincluding an alcohol, halo or other polar functional group; and whereinR₇ and R₈ can independently be —H or an alkyl group, including a methyl,ethyl, propyl, isopropyl, butyl, or pentyl group or the like, or anaromatic group; and wherein R₇ and R₈ can optionally have othersubstituents; and wherein R₂, R₃, R₄, R₅ and/or R₆ can optionally haveother substituents.
 10. The method as defined in claim 1, wherein thepolar aromatic solvent or alkyl alcohol solvent comprises acetophenone,2-ethyl-1-hexanol, 1-decanol, 2-propanol, cyclohexanol, benzyl alcohol,1-phenylethanol, benzaldehyde, methylcyclohexylketone, cyclohexanone,4′-methylacetophenone, 2′,4′-dimethylacetophenone,3′,4′-dimethylacetophenone, propiophenone, 4′-methylpropiophenone,butyrophenone, isobutyrophenone, valerophenone, 4′-hydroxyvalerophenone,hexanophenone, 2,2′-4,4′ tetrahydroxybenzophenone,2-tert-butylcyclohexylacetate, cyclohexyl phenyl ketone, isobutylbenzoate, dibenzyl ether, benzoic acid, propyl-4-hydroxybenzoate,1-nonanol, 1-dodecanol, 2-butyl-1-octanol, 2-hexyl-1-decanol, 2-octanol,3,4-dimethylbenzyl alcohol, alpha-4-dimethylbenzyl alcohol,2-phenyl-2-propanol, p-tolualdehyde, 2-hydroxy-5-methyl benzaldehyde,4′-hydroxyacetophenone, 2′-hydroxyacetophenone, 4-hydroxybenzoic acid,4-hydroxy-3-methyl benzoic acid, ethyl benzoate, benzyl benzoate,phenol, benzyl methyl ether, butyl phenyl ether, trans-anethole, ordiphenyl ether.
 11. The method as defined in claim 1, wherein thecomposition is provided as a liquid, emulsion, solid, wax, dust,fumigant, aqueous suspension, oily dispersion, paste, powder,emulsifiable concentrate, aerosol spray, wood filler, varnish, woodtreatment, furniture oil, detergent, drywall mixture, fumigating candle,caulking composition, crack and crevice filler, sealing agent, ormattress and mattress cover treatment.
 12. The method as defined inclaim 1, wherein the pests are located indoors, in or at households, inor at commercial buildings or spaces, in shipping containers, ingreenhouses, outdoors, or on agricultural land.
 13. The method asdefined in claim 1, wherein the method comprises preventing eclosion ofpest eggs by applying the composition to the eggs or to a surface wherepests may deposit their eggs.
 14. The method as defined in claim 13,wherein the pests comprise arthropods.
 15. The method as defined inclaim 14, wherein the arthropods are of the orders Blattellidae,Orthoptera, or Hemiptera.
 16. The method as defined in claim 14, whereinthe arthropods comprise bed bugs or cockroaches.
 17. The method asdefined in claim 1 comprising applying the composition directly to thepests or to surfaces where the pests or their eggs may contact orotherwise be exposed to the composition, waiting at least 7 days, 8days, 9 days, 10 days, 11 days, 12 days, 13 days, 14 days, 15 days, 16days, 17 days, 18 days, 19 days, 20 days, or 21 days, and thenre-applying the composition directly to the pests, or to surfaces wherethe pests or their eggs may contact or otherwise be exposed to thecomposition.
 18. The method as defined in claim 1, wherein the methodcomprises applying the composition in either liquid or vapor form. 19.The method as defined in claim 1, wherein the method comprises applyingthe composition to surfaces inside or at a household, residence,structure, building or other enclosed space.
 20. A method of controllingpests comprising exposing the pests or their eggs to a compositioncomprising a pesticidal natural oil and/or a component thereof and/or aderivative thereof and an aryl alcohol solvent.